Lubricating oil compositions with antioxidant formation and dissipation control

ABSTRACT

A method for controlling formation and dissipation of at least one oligomeric or polymeric aminic antioxidant in a lubricating oil, during operation of an engine or other mechanical component lubricated with the lubricating oil by using as the lubricating oil a formulated oil. The formulated oil has a composition including a lubricating oil base stock as a major component, and at least one oligomeric or polymeric aminic antioxidant, as a minor component. The at least one oligomeric or polymeric aminic antioxidant is formed over time in situ from at least one monomeric aminic antioxidant during operation of the engine or other mechanical component. The at least one oligomeric or polymeric aminic antioxidant is dissipated over time in the lubricating oil during operation of the engine or other mechanical component. The at least one monomeric aminic antioxidant is present in an amount from greater than 2 to 10 wt. % of the lubricating oil.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/781,720, filed on Dec. 19, 2018, and is also related to U.S.Provisional Application No. 62/781,751, filed on Dec. 19, 2018 theentire contents of which are incorporated herein by reference.

FIELD

This disclosure relates to engine lubricating oils with antioxidantformation and dissipation control. In particular, this disclosurerelates to lubricating oils, and methods for to controlling formationand dissipation of antioxidants in a lubricating oil in an engine orother mechanical component lubricated with the lubricating oil. Thelubricating oils of this disclosure are useful as passenger vehicleengine oil (PVEO) products, commercial vehicle engine oil (CVEO)products, or other applications where lubricating oils are subjected toheat and oxidative conditions.

BACKGROUND

Lubricant viscosity control is one of the key parameters affecting oillife, which translates in oil drain interval in practical terms.Additionally, deposit formation is an issue associated with thedecomposition of the base stock molecules mostly propagated by oxidativechain reactions. There are several conventional approaches to improveviscosity control of a finished lubricant product, including lubricatingoil additive packages.

Improved viscosity control is necessary to increase oil life and oildrain intervals, thus reducing the amount of used oil generated as aconsequence of more frequent oil changes. Longer oil life and oil drainintervals are key benefits that are desirable to end customers.Traditional additive packages provide standard protection and controlleaving the main differentiation hinging on the quality of the basestock in the formulation.

What is needed is newly designed lubricants capable of controlling oilthickening for longer periods of time as compared to conventionallubricants. Further, what is needed is newly designed lubricants thatenable extended oil life in combination with desired deposit control andcleanliness performance.

SUMMARY

This disclosure relates to engine lubricating oils with antioxidantformation and dissipation control. In particular, this disclosurerelates to lubricating oils, and methods for controlling formation anddissipation of antioxidants in a lubricating oil in an engine or othermechanical component lubricated with the lubricating oil. Thelubricating oils of this disclosure are useful as passenger vehicleengine oil (PVEO) products, commercial vehicle engine oil (CVEO)products, or other applications where lubricating oils are subjected toheat and oxidative conditions.

This disclosure also relates in part to a method for controllingformation and dissipation of at least one oligomeric or polymeric aminicantioxidant in a lubricating oil, during operation of an engine or othermechanical component lubricated with the lubricating oil by using as thelubricating oil a formulated oil. The formulated oil has a compositioncomprising a lubricating oil base stock as a major component, and atleast one oligomeric or polymeric aminic antioxidant, as a minorcomponent. The at least one oligomeric or polymeric aminic antioxidantis formed over time in situ from at least one monomeric aminicantioxidant during operation of the engine or other mechanicalcomponent. The at least one oligomeric or polymeric aminic antioxidantis dissipated over time in the lubricating oil during operation of theengine or other mechanical component. The lubricating oil base stock ispresent in an amount from about 1 to about 95 weight percent, based onthe total weight of the lubricating oil, or more preferably from about 1to about 85 weight percent, based on the total weight of the lubricatingoil, or most preferably from 70 to 95 weight percent, based on the totalweight of the lubricating oil. The at least one monomeric aminicantioxidant is present in an amount from greater than about 2 to about10 weight percent, based on the total weight of the lubricating oil.

This disclosure further relates in part to a method for controllingformation and dissipation of at least one oligomeric or polymeric aminicantioxidant in a lubricating oil, during operation of an engine or othermechanical component lubricated with the lubricating oil by using as thelubricating oil a formulated oil. The formulated oil has a compositioncomprising a lubricating oil base stock as a major component, and atleast one monomeric aminic antioxidant, as a minor component. At leastone oligomeric or polymeric aminic antioxidant is formed over time insitu from the at least one monomeric aminic antioxidant during operationof the engine or other mechanical component. The at least one oligomericor polymeric aminic antioxidant is dissipated over time in thelubricating oil during operation of the engine or other mechanicalcomponent. The lubricating oil base stock is present in an amount fromabout 1 to about 95 weight percent, based on the total weight of thelubricating oil, or more preferably from about 1 to about 85 weightpercent, based on the total weight of the lubricating oil, or mostpreferably from 70 to 95 weight percent, based on the total weight ofthe lubricating oil. The at least one monomeric aminic antioxidant ispresent in an amount from greater than about 2 to about 10 weightpercent, based on the total weight of the lubricating oil.

This disclosure yet further relates in part to a method for controllingformation and dissipation of at least one oligomeric or polymeric aminicantioxidant in a lubricating oil, during operation of an engine or othermechanical component lubricated with the lubricating oil by using as thelubricating oil a formulated oil. The formulated oil has a compositioncomprising a lubricating oil base stock as a major component, and atleast one oligomeric or polymeric aminic antioxidant and at least onemonomeric aminic antioxidant, as minor components. The at least oneoligomeric or polymeric aminic antioxidant and the at least onemonomeric aminic antioxidant react to form over time in situ at leastone oligomeric or polymeric aminic antioxidant reaction product duringoperation of the engine or other mechanical component. The at least oneoligomeric or polymeric aminic antioxidant reaction product isdissipated over time in the lubricating oil during operation of theengine or other mechanical component. The lubricating oil base stock ispresent in an amount from about 1 to about 95 weight percent, based onthe total weight of the lubricating oil, or more preferably from about 1to about 85 weight percent, based on the total weight of the lubricatingoil, or most preferably from 70 to 95 weight percent, based on the totalweight of the lubricating oil. The at least one oligomeric or polymericaminic antioxidant is present in an amount from greater than about 0.1to about 10 weight percent, based on the total weight of the lubricatingoil. The at least one monomeric aminic antioxidant is present in anamount from greater than about 2 to about 10 weight percent, based onthe total weight of the lubricating oil.

This disclosure also relates in part to a method for regenerating atleast one oligomeric or polymeric aminic antioxidant in a lubricatingoil, during operation of an engine or other mechanical componentlubricated with the lubricating oil by using as the lubricating oil aformulated oil. The formulated oil has a composition comprising alubricating oil base stock as a major component, and at least oneoligomeric or polymeric aminic antioxidant and at least one monomericaminic antioxidant, as minor components. The at least one oligomeric orpolymeric aminic antioxidant dissipates over time in the lubricating oilduring operation of the engine or other mechanical component. The atleast one oligomeric or polymeric aminic antioxidant and the at leastone monomeric aminic antioxidant react to form over time in situ atleast one regenerated oligomeric or polymeric aminic antioxidant duringoperation of the engine or other mechanical component. The lubricatingoil base stock is present in an amount from about 1 to about 95 weightpercent, based on the total weight of the lubricating oil, or morepreferably from about 1 to about 85 weight percent, based on the totalweight of the lubricating oil, or most preferably from 70 to 95 weightpercent, based on the total weight of the lubricating oil. The at leastone oligomeric or polymeric aminic antioxidant is present in an amountfrom greater than about 0.1 to about 10 weight percent, based on thetotal weight of the lubricating oil. The at least one monomeric aminicantioxidant is present in an amount from greater than about 2 to about10 weight percent, based on the total weight of the lubricating oil.

This disclosure further relates in part to a lubricating oil having acomposition comprising a lubricating oil base stock as a majorcomponent, and at least one oligomeric or polymeric aminic antioxidant,as a minor component. In an engine or other mechanical componentlubricated with the lubricating oil, the at least one oligomeric orpolymeric aminic antioxidant is formed over time in situ from at leastone monomeric aminic antioxidant during operation of the engine or othermechanical component. The at least one oligomeric or polymeric aminicantioxidant is dissipated over time in the lubricating oil duringoperation of the to engine or other mechanical component. Thelubricating oil base stock is present in an amount from about 1 to about95 weight percent, based on the total weight of the lubricating oil, ormore preferably from about 1 to about 85 weight percent, based on thetotal weight of the lubricating oil, or most preferably from 70 to 95weight percent, based on the total weight of the lubricating oil. The atleast one monomeric aminic antioxidant is present in an amount fromgreater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil.

This disclosure yet further relates in part to a lubricating oil havinga composition comprising a lubricating oil base stock as a majorcomponent, and at least one monomeric aminic antioxidant, as a minorcomponent. In an engine or other mechanical component lubricated withthe lubricating oil, at least one oligomeric or polymeric aminicantioxidant is formed over time in situ from the at least one monomericaminic antioxidant during operation of the engine or other mechanicalcomponent. The at least one oligomeric or polymeric aminic antioxidantis dissipated over time in the lubricating oil during operation of theengine or other mechanical component. The lubricating oil base stock ispresent in an amount from about 1 to about 95 weight percent, based onthe total weight of the lubricating oil, or more preferably from about 1to about 85 weight percent, based on the total weight of the lubricatingoil, or most preferably from 70 to 95 weight percent, based on the totalweight of the lubricating oil. The at least one monomeric aminicantioxidant is present in an amount from greater than about 2 to about10 weight percent, based on the total weight of the lubricating oil.

This disclosure also relates in part to a lubricating oil having acomposition comprising a lubricating oil base stock as a majorcomponent, and at least one oligomeric or polymeric aminic antioxidantand at least one monomeric aminic antioxidant, as minor components. Inan engine or other mechanical component lubricated with the lubricatingoil, the at least one oligomeric or polymeric aminic antioxidant and theat least one monomeric aminic antioxidant react to form over time insitu at least one oligomeric or polymeric aminic antioxidant reactionproduct during operation of the engine or other mechanical component.The at least one oligomeric or polymeric aminic antioxidant reactionproduct is dissipated over time in the lubricating oil during operationof the engine or other mechanical component. The lubricating oil basestock is present in an amount from about 1 to about 95 weight percent,based on the total weight of the lubricating oil, or more preferablyfrom about 1 to about 85 weight percent, based on the total weight ofthe lubricating oil, or most preferably from 70 to 95 weight percent,based on the total weight of the lubricating oil. The at least oneoligomeric or polymeric aminic antioxidant is present in an amount fromgreater than about 0.1 to about 10 weight percent, based on the totalweight of the lubricating oil. The at least one monomeric aminicantioxidant is present in an amount from greater than about 2 to about10 weight percent, based on the total weight of the lubricating oil.

This disclosure further relates in part to a lubricating oil having acomposition comprising a lubricating oil base stock as a majorcomponent, and at least one oligomeric or polymeric aminic antioxidantand at least one monomeric aminic antioxidant, as minor components. Inan engine or other mechanical component lubricated with the lubricatingoil, the at least one oligomeric or polymeric aminic antioxidantdissipates over time in the lubricating oil during operation of theengine or other mechanical component. the at least one oligomeric orpolymeric aminic antioxidant and the at least one monomeric aminicantioxidant react to form over time in situ at least one regeneratedoligomeric or polymeric aminic antioxidant during operation of theengine or other mechanical component. The lubricating oil base stock ispresent in an amount from about 1 to about 95 weight percent, based onthe total weight of the lubricating oil, or more preferably from about 1to about 85 weight percent, based on the total weight of the lubricatingoil, or most preferably from 70 to 95 weight percent, based on the totalweight of the lubricating oil. The at least one oligomeric or polymericaminic antioxidant is present in an amount from greater than about 0.1to about 10 weight percent, based on the total weight of the lubricatingoil. The at least one monomeric aminic antioxidant is present in anamount from greater than about 2 to about 10 weight percent, based onthe total weight of the lubricating oil.

It has been surprisingly found that, in accordance with this disclosure,oligomeric or polymeric aminic antioxidant formation and dissipationcontrol in lubricating oils is improved using high treat rates ofmonomeric aminic antioxidants in lubricating oils, as compared tooligomeric or polymeric aminic antioxidant formation and dissipationcontrol in lubricating oils achieved using low treat rates of monomericaminic antioxidants in lubricating oils.

In particular, it has been surprisingly found that, in measurements ofthe lubricating oil by a Sequence IIIH engine test in accordance withASTM D8111-17, oligomeric or polymeric aminic antioxidant formation anddissipation control are improved using a concentration of monomericaminic antioxidant from greater than about 2 to about 10 weight percent,based on the total weight of the lubricating oil, as compared tooligomeric or polymeric aminic antioxidant formation and dissipationcontrol achieved using a lower concentration of the monomeric aminicantioxidant. The controlled release/in situ generation of oligomeric andpolymeric antioxidants in the lubricating oils, which result from aconcentration of monomeric aminic antioxidant from greater than about 2to about 10 weight percent, based on the total weight of the lubricatingoil, leads to surprisingly exceptional performance in the Sequence IIIHengine test.

Other objects and advantages of the present disclosure will becomeapparent from the detailed description that follows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows ion counts for oligomers of Irganox® L57 in comparativeExample 1 formulated oil analyzed by liquid chromatography massspectrometry (LCMS).

FIG. 2 shows ion counts for oligomers of Irganox® L57 in inventiveExample 2 formulated oil analyzed by LCMS.

DETAILED DESCRIPTION Definitions

“About” or “approximately.” All numerical values within the detaileddescription and the claims herein are modified by “about” or“approximately” the indicated value, and take into account experimentalerror and variations that would be expected by a person having ordinaryskill in the art.

“Major amount” as it relates to components included within thelubricating oils of the specification and the claims means greater thanor equal to 50 wt. %, or greater than or equal to 60 wt. %, or greaterthan or equal to 70 wt. %, or greater than or equal to 80 wt. %, orgreater than or equal to 90 wt. % based on the total weight of thelubricating oil.

“Minor amount” as it relates to components included within thelubricating oils of the specification and the claims means less than 50wt. %, or less than or equal to 40 wt. %, or less than or equal to 30wt. %, or greater than or equal to 20 wt. %, or less than or equal to 10wt. %, or less than or equal to 5 wt. %, or less than or equal to 2 wt.%, or less than or equal to 1 wt. %, based on the total weight of thelubricating oil.

“Essentially free” as it relates to components included within thelubricating oils of the specification and the claims means that theparticular component is at 0 weight % within the lubricating oil, oralternatively is at impurity type levels within the lubricating oil(less than 100 ppm, or less than 20 ppm, or less than 10 ppm, or lessthan 1 ppm).

“Other lubricating oil additives” as used in the specification and theclaims means other lubricating oil additives that are not specificallyrecited in the particular section of the specification or the claims.For example, other lubricating oil additives may include, but are notlimited to, antioxidants, detergents, dispersants, antiwear additives,corrosion inhibitors, viscosity modifiers, metal passivators, pour pointdepressants, seal compatibility agents, antifoam agents, extremepressure agents, friction modifiers and combinations thereof.

“Other mechanical component” as used in the specification and the claimsmeans an electric vehicle component, a hybrid vehicle component, a powertrain, a driveline, a transmission, a gear, a gear train, a gear set, acompressor, a pump, a hydraulic system, a bearing, a bushing, a turbine,a piston, a piston ring, a cylinder liner, a cylinder, a cam, a tappet,a lifter, a gear, a valve, or a bearing including a journal, a roller, atapered, a needle, and a ball bearing.

“Hydrocarbon” refers to a compound consisting of carbon atoms andhydrogen atoms.

“Alkane” refers to a hydrocarbon that is completely saturated. An alkanecan be linear, branched, cyclic, or substituted cyclic.

“Olefin” refers to a non-aromatic hydrocarbon comprising one or morecarbon-carbon double bond in the molecular structure thereof.

“Mono-olefin” refers to an olefin comprising a single carbon-carbondouble bond.

“Cn” group or compound refers to a group or a compound comprising carbonatoms at total number thereof of n. Thus, “Cm-Cn” group or compoundrefers to a group or compound comprising carbon atoms at a total numberthereof in the range from m to n. Thus, a C1-C50 alkyl group refers toan alkyl group comprising carbon atoms at a total number thereof in therange from 1 to 50.

“Carbon backbone” refers to the longest straight carbon chain in themolecule of the compound or the group in question. “Branch” refer to anysubstituted or unsubstituted hydrocarbyl group connected to the carbonbackbone. A carbon atom on the carbon backbone connected to a branch iscalled a “branched carbon.”

“Epsilon-carbon” in a branched alkane refers to a carbon atom in itscarbon backbone that is (i) connected to two hydrogen atoms and twocarbon atoms and (ii) connected to a branched carbon via at least four(4) methylene (CH₂) groups. Quantity of epsilon carbon atoms in terms ofmole percentage thereof in a alkane material based on the total moles ofcarbon atoms can be determined by using, e.g., ¹³C NMR.

“Alpha-carbon” in a branched alkane refers to a carbon atom in itscarbon backbone that is with a methyl end with no branch on the first 4carbons. It is also measured in mole percentage using ¹³C NMR.

“T/P methyl” in a branched alkane refers to a methyl end and a methyl inthe 2 position. It is also measured in mole percentage using ¹³C NMR.

“P-methyl” in a branched alkane refers to a methyl branch anywhere onthe chain, except in the 2 position. It is also measured in molepercentage using ¹³C NMR.

“SAE” refers to SAE International, formerly known as Society ofAutomotive Engineers, which is a professional organization that setsstandards for internal combustion engine lubricating oils.

“SAE J300” refers to the viscosity grade classification system of enginelubricating oils established by SAE, which defines the limits of theclassifications in rheological terms only.

“Base stock” or “base oil” interchangeably refers to an oil that can beused as a component of lubricating oils, heat transfer oils, hydraulicoils, grease products, and the like.

“Lubricating oil” or “lubricant” interchangeably refers to a substancethat can be introduced between two or more surfaces to reduce the levelof friction between two adjacent surfaces moving relative to each other.A lubricant base stock is a material, typically a fluid at variouslevels of viscosity at the operating temperature of the lubricant, usedto formulate a lubricant by admixing with other components. Non-limitingexamples of base stocks suitable in lubricants include API Group I,Group II, Group III, Group IV, and Group V base stocks. PAOs,particularly hydrogenated PAOs, have recently found wide use inlubricants as a Group IV base stock, and are particularly preferred. Ifone base stock is designated as a primary base stock in the lubricant,additional base stocks may be called a co-base stock.

All kinematic viscosity values in this disclosure are as determinedpursuant to ASTM D445. Kinematic viscosity at 100° C. is reported hereinas KV100, and kinematic viscosity at 40° C. is reported herein as KV40.Unit of all KV100 and KV40 values herein is cSt unless otherwisespecified. When describing the kinematic viscosity at 100° C. is“essentially” maintained, the kinematic viscosity at 100° C. is expectedto vary less than 0.2 cSt as measured by ASTM D445.

All viscosity index (“VI”) values in this disclosure are as determinedpursuant to ASTM D2270.

All Noack volatility (“NV”) values in this disclosure are as determinedpursuant to ASTM D5800 unless specified otherwise. Unit of all NV valuesis wt %, unless otherwise specified.

All pour point values in this disclosure are as determined pursuant toASTM D5950 or D97.

All CCS viscosity (“CCSV”) values in this disclosure are as determinedpursuant to ASTM 5293. Unit of all CCSV values herein is millipascalsecond (mPa·s), which is equivalent to centipoise), unless specifiedotherwise. All CCSV values are measured at a temperature of interest tothe lubricating oil formulation or oil composition in question. Thus,for the purpose of designing and fabricating engine oil formulations,the temperature of interest is the temperature at which the SAE J300imposes a minimal CCSV.

All percentages in describing chemical compositions herein are by weightunless specified otherwise. “Wt.%” means percent by weight.

Lubricating Oil Compositions of This Disclosure

This disclosure describes the controlled in situ generation of powerfuloligomeric or polymeric antioxidants in the engine of a passengervehicle, commercial vehicle, a fired engine, or other mechanicalcomponent.

Antioxidants are critical to delivering viscosity control over theentire oil drain interval. This disclosure describes the in situgeneration of oligomeric and polymeric antioxidants from conventionalmonomeric aminic antioxidants during normal engine use. This disclosurealso describes the controlled in situ regeneration of commercialoligomeric and polymeric antioxidants during engine use, byco-formulating them in situ with conventional aminic antioxidants.

Further, in accordance with this disclosure, finished lubricants can bedesigned with in situ generated oligomeric and polymeric antioxidantsthat are capable of controlling oil thickening for long durations ascompared to conventional lubricants. This disclosure also enablesextended oil life in combination with superior deposit control andcleanliness performance through the in situ generation of oligomeric andpolymeric antioxidants.

This disclosure describes the superior performance of conventionalmonomeric aminic antioxidants in lubricating oils. It also allows forthe in situ production of oligomeric and polymeric antioxidants from themonomeric aminic antioxidants during engine use. It further allows for areduction of the treat rate of the oligomeric and polymericantioxidants, replacing the balance with traditional monomeric aminicantioxidants which can react in situ to form oligomeric and polymericantioxidants and which come at a lower cost and result in a moreacceptable formulation appearance/color.

In general, formulators use low treat rates of aminic antioxidants (<2wt %, and often less than 1 wt %) such as Irganox L57 or Irganox L67 inpassenger vehicle formulations. In accordance with this disclosure, ithas been found that at a high enough treat rate (5 wt % for example),monomeric aminic antioxidants can form analogous oligomers and polymersduring the course of a Sequence IIIH engine test resulting in superiorperformance in respect to viscosity control (see FIG. 1) and cleanliness(see FIG. 2).

In measurements of the lubricating oil by a Sequence IIIH engine test inaccordance with ASTM D8111-17, oligomeric or polymeric aminicantioxidant formation and dissipation control are improved using hightreat rates (e.g., 5 wt %) of monomeric aminic antioxidants as comparedto oligomeric or polymeric aminic antioxidant formation and dissipationcontrol achieved using low treat rates (e.g., 2 wt %) of monomericaminic antioxidants. The controlled release/in situ generation ofoligomeric and polymeric antioxidants in the lubricating oils, whichresult from the high treat rates (e.g., 5 wt %) of monomeric aminicantioxidants, leads to exceptional performance in the Sequence IIIHengine test.

Lubricating Oil Base Stocks

A wide range of lubricating base oils is known in the art. Lubricatingbase oils that are useful in the present disclosure are both naturaloils, and synthetic oils, and unconventional oils (or mixtures thereof)can be used unrefined, refined, or rerefined (the latter is also knownas reclaimed or reprocessed oil). Unrefined oils are those obtaineddirectly from a natural or synthetic source and used without addedpurification. These include shale oil obtained directly from retortingoperations, petroleum oil obtained directly from primary distillation,and ester oil obtained directly from an esterification process. Refinedoils are similar to the oils discussed for unrefined oils except refinedoils are subjected to one or more purification steps to improve at leastone lubricating oil property. One skilled in the art is familiar withmany purification processes. These processes include solvent extraction,secondary distillation, acid extraction, base extraction, filtration,and percolation. Rerefined oils are obtained by processes analogous torefined oils but using an oil that has been previously used as a feedstock.

Groups I, II, III, IV and V are broad base oil stock categoriesdeveloped and defined by the American Petroleum Institute (APIPublication 1509; www.API.org) to create guidelines for lubricant baseoils. Group I base stocks have a viscosity index of between about 80 to120 and contain greater than about 0.03% sulfur and/or less than about90% saturates. Group II base stocks have a viscosity index of betweenabout 80 to 120, and contain less than or equal to about 0.03% sulfurand greater than or equal to about 90% saturates. Group III stocks havea viscosity index greater than about 120 and contain less than or equalto about 0.03% sulfur and greater than about 90% saturates. Group IVincludes polyalphaolefins (PAO). Group V base stock includes base stocksnot included in Groups I-IV. The table below summarizes properties ofeach of these five groups.

Base Oil Properties Saturates Sulfur Viscosity Index Group I <90and/or >0.03% and ≥80 and <120 Group II ≥90 and ≤0.03% and ≥80 and <120Group III ≥90 and ≤0.03% and ≥120 Group IV Polyalphaolefins (PAO) GroupV All other base oil stocks not included in Groups I, II, III or IV

Natural oils include animal oils, vegetable oils (castor oil and lardoil, for example), and mineral oils. Animal and vegetable oilspossessing favorable thermal oxidative stability can be used. Of thenatural oils, mineral oils are preferred. Mineral oils vary widely as totheir crude source, for example, as to whether they are paraffinic,naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal orshale are also useful. Natural oils vary also as to the method used fortheir production and purification, for example, their distillation rangeand whether they are straight run or cracked, hydrorefined, or solventextracted.

Group II and/or Group III hydroprocessed or hydrocracked base stocks,including synthetic oils such as polyalphaolefins, alkyl aromatics andsynthetic esters are also well known base stock oils.

Synthetic oils include hydrocarbon oil. Hydrocarbon oils include oilssuch as polymerized and interpolymerized olefins (polybutylenes,polypropylenes, propylene isobutylene copolymers, ethylene-olefincopolymers, and ethylene-alphaolefin copolymers, for example).Polyalphaolefin (PAO) oil base stocks are commonly used synthetichydrocarbon oil. By way of example, PAOs derived from C₈, C₁₀, C₁₂, C₁₄olefins or mixtures thereof may be utilized. See U.S. Pat. Nos.4,956,122; 4,827,064; and 4,827,073.

The number average molecular weights of the PAOs, which are knownmaterials and generally available on a major commercial scale fromsuppliers such as ExxonMobil Chemical Company, Chevron Phillips ChemicalCompany, BP, and others, typically vary from about 250 to about 3,000,although PAO's may be made in viscosities up to about 150 cSt (100° C.).The PAOs are typically comprised of relatively low molecular weighthydrogenated polymers or oligomers of alphaolefins which include, butare not limited to, C₂ to about C₃₂ alphaolefins with the C₈ to aboutC₁₆ alphaolefins, such as 1-hexene, 1-octene, 1-decene, 1-dodecene andthe like, being preferred. The preferred polyalphaolefins arepoly-1-hexene, poly-1-octene, poly-1-decene and poly-1-dodecene andmixtures thereof and mixed olefin-derived polyolefins. However, thedimers of higher olefins in the range of C₁₄ to C₁₈ may be used toprovide low viscosity base stocks of acceptably low volatility.Depending on the viscosity grade and the starting oligomer, the PAOs maybe predominantly trimers and tetramers of the starting olefins, withminor amounts of the higher oligomers, having a viscosity range of 1.5to 12 cSt. PAO fluids of particular use may include 3.0 cSt, 3.4 cSt,and/or 3.6 cSt and combinations thereof. Bi-modal mixtures of PAO fluidshaving a viscosity range of 1.5 to 150 cSt may be used if desired.

The PAO fluids may be conveniently made by the polymerization of analphaolefin in the presence of a polymerization catalyst such as theFriedel-Crafts catalysts including, for example, aluminum trichloride,boron trifluoride or complexes of boron trifluoride with water, alcoholssuch as ethanol, propanol or butanol, carboxylic acids or esters such asethyl acetate or ethyl propionate. For example the methods disclosed byU.S. Pat. No. 4,149,178 or 3,382,291 to may be conveniently used herein.Other descriptions of PAO synthesis are found in the following U.S. Pat.Nos. 3,742,082; 3,769,363; 3,876,720; 4,239,930; 4,367,352; 4,413,156;4,434,408; 4,910,355; 4,956,122; and 5,068,487. The dimers of the C₁₄ toC₁₈ olefins are described in U.S. Pat. No. 4,218,330.

The alkylated naphthalene can be used as base oil or base oil componentand can be any hydrocarbyl molecule that contains at least about 5% ofits weight derived from a naphthenoid moiety, or its derivatives. Thesealkylated naphthalenes include alkyl naphthalenes, alkyl naphthols, andthe like. The naphthenoid group can be mono-alkylated, dialkylated,polyalkylated, and the like. The naphthenoid group can be mono- orpoly-functionalized. The naphthenoid group can also be derived fromnatural (petroleum) sources, provided at least about 5% of the moleculeis comprised of the naphthenoid moiety. Viscosities at 100° C. ofapproximately 3 cSt to about 50 cSt are preferred, with viscosities ofapproximately 3.4 cSt to about 20 cSt often being more preferred for thenaphthylene component. In one embodiment, an alkyl naphthalene where thealkyl group is primarily comprised of 1-hexadecene is used. Otheralkylates of naphthalene can be advantageously used. Naphthalene ormethyl naphthalene, for example, can be alkylated with olefins such asoctene, decene, dodecene, tetradecene or higher, mixtures of similarolefins, and the like.

Alkylated naphthalenes of the present disclosure may be produced bywell-known Friedel-Crafts alkylation of aromatic compounds. SeeFriedel-Crafts and Related Reactions, Olah, G. A. (ed.), Inter-sciencePublishers, New York, 1963. For example, an aromatic compound, such asnaphthalene, is alkylated by an olefin, alkyl halide or alcohol in thepresence of a Friedel-Crafts catalyst. See Friedel-Crafts and RelatedReactions, Vol. 2, part 1, chapters 14, 17, and 18, See Olah, G. A.(ed.), Inter-science Publishers, New York, 1964. Many homogeneous orheterogeneous, solid catalysts are known to one skilled in the art. Thechoice of catalyst depends on the reactivity of the starting materialsand product quality requirements. For example, strong acids such asAlCl₃, BF₃, or HF may be used. In some cases, milder catalysts such asFeCl₃ or SnCl₄ are preferred. Newer alkylation technology uses zeolitesor solid super acids.

Mixtures of alkylated naphthalene base stocks with other lubricating oilbase stocks (e.g., Groups I, II, III, IV and V base stocks) may beuseful in the lubricating oil formulations of this disclosure.

The alkylated naphthalene can be present in an amount of from about 30to about 99.8 weight percent, or from about 35 to about 95 weightpercent, or from about 40 to about 90 weight percent, or from about 45to about 85 weight percent, or from about 50 to about 80 weight percent,or from about 55 to about 75 weight percent, or from about 60 to about70 weight percent, based on the total weight of the formulated oil.

Other useful lubricant oil base stocks include wax isomerate base stocksand base oils, comprising hydroisomerized waxy stocks (e.g. waxy stockssuch as gas oils, slack waxes, fuels hydrocracker bottoms, etc.),hydroisomerized Fischer-Tropsch waxes, Gas-to-Liquids (GTL) base stocksand base oils, and other wax isomerate hydroisomerized base stocks andbase oils, or mixtures thereof Fischer-Tropsch waxes, the high boilingpoint residues of Fischer-Tropsch synthesis, are highly paraffinichydrocarbons with very low sulfur content. The hydroprocessing used forthe production of such base stocks may use an amorphoushydrocracking/hydroisomerization catalyst, such as one of thespecialized lube hydrocracking (LHDC) catalysts or a crystallinehydrocracking/hydroisomerization catalyst, preferably a zeoliticcatalyst. For example, one useful catalyst is ZSM-48 as described inU.S. Pat. No. 5,075,269, the disclosure of which is incorporated hereinby reference in its entirety. Processes for makinghydrocracked/hydroisomerized distillates andhydrocracked/hydroisomerized waxes are described, for example, in U.S.Pat. Nos. 2,817,693; 4,975,177; 4,921,594 and 4,897,178 as well as inBritish Patent Nos. 1,429,494; 1,350,257; 1,440,230 and 1,390,359. Eachof the aforementioned patents is incorporated herein in their entirety.Particularly favorable processes are described in European PatentApplication Nos. 464546 and 464547, also incorporated herein byreference. Processes using Fischer-Tropsch wax feeds are described inU.S. Pat. Nos. 4,594,172 and 4,943,672, the disclosures of which areincorporated herein by reference in their entirety.

Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils,and other wax-derived hydroisomerized (wax isomerate) base oils beadvantageously used in the instant disclosure, and may have usefulkinematic viscosities at 100° C. of about 3 cSt to about 50 cSt,preferably about 3 cSt to about 30 cSt, more preferably about 3.5 cSt toabout 25 cSt, as exemplified by GTL 4 with kinematic viscosity of about4.0 cSt at 100° C. and a viscosity index of about 141. TheseGas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived base oils,and other wax-derived hydroisomerized base oils may have useful pourpoints of about −20° C. or lower, and under some conditions may haveadvantageous pour points of about −25° C. or lower, with useful pourpoints of about −30° C. to about −40° C. or lower. Useful compositionsof Gas-to-Liquids (GTL) base oils, Fischer-Tropsch wax derived baseoils, and wax-derived hydroisomerized base oils are recited in U.S. Pat.Nos. 6,080,301; 6,090,989, and 6,165,949 for example, and areincorporated herein in their entirety by reference.

The hydrocarbyl aromatics can be used as base oil or base oil componentand can be to any hydrocarbyl molecule that contains at least about 5%of its weight derived from an aromatic moiety such as a benzenoid moietyor naphthenoid moiety, or their derivatives. These hydrocarbyl aromaticsinclude alkyl benzenes, alkyl naphthalenes, alkyl diphenyl oxides, alkylnaphthols, alkyl diphenyl sulfides, alkylated bis-phenol A, alkylatedthiodiphenol, and the like. The aromatic can be mono-alkylated,dialkylated, polyalkylated, and the like. The aromatic can be mono- orpoly-functionalized. The hydrocarbyl groups can also be comprised ofmixtures of alkyl groups, alkenyl groups, alkynyl, cycloalkyl groups,cycloalkenyl groups and other related hydrocarbyl groups. Thehydrocarbyl groups can range from about C₆ up to about C₆₀ with a rangeof about C₈ to about C₂₀ often being preferred. A mixture of hydrocarbylgroups is often preferred, and up to about three such substituents maybe present. The hydrocarbyl group can optionally contain sulfur, oxygen,and/or nitrogen containing substituents. The aromatic group can also bederived from natural (petroleum) sources, provided at least about 5% ofthe molecule is comprised of an above-type aromatic moiety. Viscositiesat 100° C. of approximately 3 cSt to about 50 cSt are preferred, withviscosities of approximately 3.4 cSt to about 20 cSt often being morepreferred for the hydrocarbyl aromatic component. In one embodiment, analkyl naphthalene where the alkyl group is primarily comprised of1-hexadecene is used. Other alkylates of aromatics can be advantageouslyused. Naphthalene or methyl naphthalene, for example, can be alkylatedwith olefins such as octene, decene, dodecene, tetradecene or higher,mixtures of similar olefins, and the like. Useful concentrations ofhydrocarbyl aromatic in a lubricant oil composition can be about 2% toabout 25%, preferably about 4% to about 20%, and more preferably about4% to about 15%, depending on the application.

Alkylated aromatics such as the hydrocarbyl aromatics of the presentdisclosure may be produced by well-known Friedel-Crafts alkylation ofaromatic compounds. See Friedel-Crafts and Related Reactions, Olah, G.A. (ed.), Inter-science Publishers, New York, 1963. For example, anaromatic compound, such as benzene or naphthalene, is alkylated by anolefin, alkyl halide or alcohol in the presence of a Friedel-Craftscatalyst. See Friedel-Crafts and Related Reactions, Vol. 2, part 1,chapters 14, 17, and 18, See Olah, G. A. (ed.), Inter-sciencePublishers, New York, 1964. Many homogeneous or heterogeneous, solidcatalysts are known to one skilled in the art. The choice of catalystdepends on the reactivity of the starting materials and product qualityrequirements. For example, strong acids such as AlCl₃, BF₃, or HF may beused. In some cases, milder catalysts such as FeCl₃ or SnCl₄ arepreferred. Newer alkylation technology uses zeolites or solid superacids.

Other useful fluids of lubricating viscosity include non-conventional orunconventional base stocks that have been processed, preferablycatalytically, or synthesized to provide high performance lubricationcharacteristics.

Non-conventional or unconventional base stocks/base oils include one ormore of a mixture of base stock(s) derived from one or moreGas-to-Liquids (GTL) materials, as well as isomerate/isodewaxate basestock(s) derived from natural wax or waxy feeds, mineral and ornon-mineral oil waxy feed stocks such as slack waxes, natural waxes, andwaxy stocks such as gas oils, waxy fuels hydrocracker bottoms, waxyraffinate, hydrocrackate, thermal crackates, or other mineral, mineraloil, or even non-petroleum oil derived waxy materials such as waxymaterials received from coal liquefaction or shale oil, and mixtures ofsuch base stocks.

GTL materials are materials that are derived via one or more synthesis,combination, transformation, rearrangement, and/ordegradation/deconstructive processes from gaseous carbon-containingcompounds, hydrogen-containing compounds and/or elements as feed stockssuch as hydrogen, carbon dioxide, carbon monoxide, water, methane,ethane, ethylene, acetylene, propane, propylene, propyne, butane,butylenes, and butynes. GTL base stocks and/or base oils are GTLmaterials of lubricating viscosity that are generally derived fromhydrocarbons; for example, waxy synthesized hydrocarbons, that arethemselves derived from simpler gaseous carbon-containing compounds,hydrogen-containing compounds and/or elements as feed stocks.

GTL base stock(s) and/or base oil(s) include oils boiling in the lubeoil boiling range (1) separated/fractionated from synthesized GTLmaterials such as, for example, by distillation and subsequentlysubjected to a final wax processing step which involves either or bothof a catalytic dewaxing process, or a solvent dewaxing process, toproduce lube oils of reduced/low pour point; (2) synthesized waxisomerates, comprising, for example, hydrodewaxed or hydroisomerized catand/or solvent dewaxed synthesized wax or waxy hydrocarbons; (3)hydrodewaxed or hydroisomerized cat and/or solvent dewaxedFischer-Tropsch (F-T) material (i.e., hydrocarbons, waxy hydrocarbons,waxes and possible analogous oxygenates); preferably hydrodewaxed orhydroisomerized/followed by cat and/or solvent dewaxing dewaxed F-T waxyhydrocarbons, or hydrodewaxed or hydroisomerized/followed by cat (orsolvent) dewaxing dewaxed, F-T waxes, or mixtures thereof.

GTL base stock(s) and/or base oil(s) derived from GTL materials,especially, hydrodewaxed or hydroisomerized/followed by cat and/orsolvent dewaxed wax or waxy feed, preferably F-T material derived basestock(s) and/or base oil(s), are characterized typically as havingkinematic viscosities at 100° C. of from about 2 mm²/s to about 50 mm²/s(ASTM D445). They are further characterized typically as having pourpoints of −5° C. to about −40° C. or lower (ASTM D97). They are alsocharacterized typically as having viscosity indices of about 80 to about140 or greater (ASTM D2270).

In addition, the GTL base stock(s) and/or base oil(s) are typicallyhighly paraffinic (>90% saturates), and may contain mixtures ofmonocycloparaffins and multicycloparaffins in combination withnon-cyclic isoparaffins. The ratio of the naphthenic (i.e.,cycloparaffin) content in such combinations varies with the catalyst andtemperature used. Further, GTL base stock(s) and/or base oil(s)typically have very low sulfur and nitrogen content, generallycontaining less than about 10 ppm, and more typically less than about 5ppm of each of these elements. The sulfur and nitrogen content of GTLbase stock(s) and/or base oil(s) obtained from F-T material, especiallyF-T wax, is essentially nil. In addition, the absence of phosphorous andaromatics make this materially especially suitable for the formulationof low SAP products.

The term GTL base stock and/or base oil and/or wax isomerate base stockand/or base oil is to be understood as embracing individual fractions ofsuch materials of wide viscosity range as recovered in the productionprocess, mixtures of two or more of such fractions, as well as mixturesof one or two or more low viscosity fractions with one, two or morehigher viscosity fractions to produce a blend wherein the blend exhibitsa target kinematic viscosity.

The GTL material, from which the GTL base stock(s) and/or base oil(s)is/are derived is preferably an F-T material (i.e., hydrocarbons, waxyhydrocarbons, wax).

Base oils for use in the formulated lubricating oils useful in thepresent disclosure are any of the variety of oils corresponding to APIGroup I, Group II, Group III, Group IV, and Group V oils and mixturesthereof, preferably API Group II, Group III, Group IV, and Group V oilsand mixtures thereof, more preferably the Group III to Group V base oilsdue to their exceptional volatility, stability, viscometric andcleanliness features.

This other base oil typically is present in an amount ranging from about0.1 to about 90 weight percent, or from about 1 to about 80 weightpercent, or from about 1 to about 70 weight percent, or from about 1 toabout 60 weight percent, or from about 1 to about 50 weight percent,based on the total weight of the composition. The base oil may beselected from any of the synthetic or natural oils typically used ascrankcase lubricating oils for spark ignition and compression-ignitedengines. The base oil conveniently has a kinematic viscosity, accordingto ASTM standards, of about 2.5 cSt to about 12 cSt (or mm²/s) at 100°C. and preferably of about 2.5 cSt to about 9 cSt (or mm²/s) at 100° C.Mixtures of synthetic and natural base oils may be used if desired.Mixtures of Group III, IV, and V may be preferable.

Oligomeric and Polymeric Aminic Antioxidants

Illustrative oligomeric and polymeric aminic antioxidants includeoligomerization and polymerization reaction products of one or moreunsubstituted or hydrocarbyl-substituted diphenyl amines, one or moreunsubstituted or hydrocarbyl-substituted phenyl naphthyl amines or bothone or more of unsubstituted or hydrocarbyl-substituted diphenylaminewith one or more unsubstituted or hydrocarbyl-substituted phenylnaphthylamine. A representative schematic is presented below:

wherein (A) and (B) each range from zero to 10, preferably zero to 5,more preferably zero to 3, most preferably 1 to 3, provided (A)+(B) isat least 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached; for example:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, preferably R² is a C1 to C30alkyl, R³ is a C1 to C30 alkyl, R⁴ is a C1 to C30 alkyl, more preferablyR² is a C4 to C10 alkyl, R³ is a C4 to C10 alkyl and R⁴ is a C4 to C10alkyl, p, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached, preferably atleast one of p, q and y range from 1 to up to the valence of the arylgroup to which the respective R group(s) are attached, more preferablyp, q and y each individually range from at least 1 to up to the valenceof the aryl group to which the respective R groups are attached.

In a preferred embodiment, the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct formed by any combination of (A) and (B) above including, butnot limited to, (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A),(B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B),(B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A)(A)(B)(B)(B)(A), and the like.

In another preferred embodiment, the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₄H₉; and/or

In a further preferred embodiment, the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product formed by any combination of:

In yet a further preferred embodiment, the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product formed by any combination of:

Other more extensive oligomers and polymers are within the scope of thisdisclosure, but materials of formulae (a), (b), (c) and (d) arepreferred.

The oligomeric or polymeric aminic antioxidant may containnonpolymerized aryl amine antioxidant starting materials as a result ofthe preparation procedure. Additional monomeric amine antioxidants maybe added to the lubricant to impart desired properties. Examples ofmonomeric amine antioxidants include but are not limited to diphenylamine, alkylated diphenyl amines, styrenated diphenyl amines,phenyl-N-naphthyl amine, alkylated phenyl-N-naphthyl amines, styrenatedphenyl-N-naphthyl amines, phenothiazine, alkylated phenothiazine, andstyrenated phenothiazine. Other antioxidants such as hindered phenolsand zinc dithiophosphates can also be added to the lubricant in additionto the polymerized amine antioxidant.

The oligomeric and polymeric aminic antioxidants useful in thisdisclosure can be prepared by conventional polymerization reactions.See, for example, U.S. Pat. Nos. 6,426,324 and 8,623,795. Anillustrative polymerization reaction for preparing preferred oligomericand polymeric aminic antioxidants useful in this disclosure is set forthbelow. The product of the reaction can yield more than the two oligomersshown below, for example, any combination of (A) and (B) belowincluding, but not limited to, (A)(A), (A)(B), (B)(B), (A)(A)(B),(A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), and the like.

The oligomeric or polymeric aminic antioxidant is present in an amountin the range 0.1 to 10 wt % (active ingredient), preferably 0.1 to 5 wt% (active ingredient), or 0.1 to 4 wt % (active ingredient), or 0.1 to2.5 wt % (active ingredient) or 0.1 to 1.5 wt % (active ingredient), orto 1.5 to 4 wt % (active ingredient), of oligomerized or polymerizedaminic antioxidant exclusive of any added antioxidants.

Monomeric Aminic Antioxidants

Illustrative monomeric aminic antioxidants useful in this disclosureinclude one or more unsubstituted or hydrocarbyl-substituted diphenylamines, one or more unsubstituted or hydrocarbyl-substituted phenylnaphthyl amines or both one or more of unsubstituted orhydrocarbyl-substituted diphenylamine and one or more unsubstituted orhydrocarbyl-substituted phenyl naphthylamine.

Preferred monomeric aminic antioxidants useful in this disclosureinclude:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

In a further preferred embodiment, the at least one monomeric aminicantioxidant can include:

In yet a further preferred embodiment, the at least one monomeric aminicantioxidant can include:

Additional monomeric amine antioxidants may be added to the lubricant toimpart desired properties. Examples of monomeric amine antioxidantsinclude but are not limited to diphenyl amine, alkylated diphenylamines, styrenated diphenyl amines, phenyl-N-naphthyl amine, alkylatedphenyl-N-naphthyl amines, styrenated phenyl-N-naphthyl amines,phenothiazine, alkylated phenothiazine, and styrenated phenothiazine.

Monomeric amine antioxidants include unsubstituted orhydrocarbon-substituted diphenyl amines, unsubstituted orhydrocarbyl-substituted phenyl naphthyl amines and unsubstituted orhydrocarbyl-substituted phenothiazines wherein thehydrocarbyl-substituted to group is styrene or a C1 to C30 alkyl group,preferably a C1 to C10 alkyl group, more preferably a C4 to C10 alkylgroup. Other monomeric aryl amines have been described in the patentliterature.

The monomeric aminic antioxidants useful in this disclosure can beprepared by conventional polymerization reactions. See, for example,U.S. Pat. Nos. 6,426,324 and 8,623,795.

The monomeric aminic antioxidant is present in an amount in the range0.1 to 10 wt % (active ingredient), preferably 0.1 to 8 wt % (activeingredient), or 0.1 to 7.5 wt % (active ingredient), or 0.1 to 5 wt %(active ingredient) or 0.1 to 2.5 wt % (active ingredient), or 1.5 to 5wt % (active ingredient), of monomeric aminic antioxidant exclusive ofany added antioxidants.

Preferably, the monomeric aminic antioxidant is present in an amount inthe range greater than about 2 to 10 wt % (active ingredient),preferably 2.5 to 9.5 wt % (active ingredient), or 3 to 9 wt % (activeingredient), or 3.5 to 8.5 wt % (active ingredient), or 4 to 8 wt %(active ingredient), or 4.5 to 7.5 wt % (active ingredient), or 5 to 7wt % (active ingredient), or 5 to 6 wt % (active ingredient), ofmonomeric aminic antioxidant exclusive of any added antioxidants.

Other Additives

The formulated lubricating oil useful in the present disclosure mayadditionally contain one or more of the other commonly used lubricatingoil performance additives including but not limited to dispersants,detergents, other antioxidants, antiwear additives, corrosioninhibitors, rust inhibitors, metal deactivators, extreme pressureadditives, anti-seizure agents, wax modifiers, viscosity indeximprovers, viscosity modifiers, fluid-loss additives, seal compatibilityagents, friction modifiers, lubricity agents, anti-staining agents,chromophoric agents, defoamants, demulsifiers, emulsifiers, densifiers,wetting agents, gelling agents, tackiness agents, colorants, and others.For a review of many commonly used additives, see Klamann in Lubricantsand Related Products, Verlag Chemie, Deerfield Beach, Fla.; ISBN0-89573-177-0. Reference is also made to “Lubricant Additives” by M. W.Ranney, published by Noyes Data Corporation of Parkridge, N J (1973);see also U.S. Pat. No. 7,704,930, the disclosure of which isincorporated herein in its entirety. These additives are commonlydelivered with varying amounts of diluent oil, that may range from 5weight percent to 50 weight percent.

Dispersants

During engine operation, oil-insoluble oxidation byproducts areproduced. Dispersants help keep these byproducts in solution, thusdiminishing their deposition on metal surfaces. Dispersants used in theformulation of the lubricating oil may be ashless or ash-forming innature. Preferably, the dispersant is ashless. So called ashlessdispersants are organic materials that form substantially no ash uponcombustion. For example, non-metal-containing or borated metal-freedispersants are considered ashless. In contrast, metal-containingdetergents discussed above form ash upon combustion.

Suitable dispersants typically contain a polar group attached to arelatively high molecular weight hydrocarbon chain. The polar grouptypically contains at least one element of nitrogen, oxygen, orphosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

A particularly useful class of dispersants are the (poly)alkenylsuccinicderivatives, typically produced by the reaction of a long chainhydrocarbyl substituted succinic compound, usually a hydrocarbylsubstituted succinic anhydride, with a polyhydroxy or polyaminocompound. The long chain hydrocarbyl group constituting the oleophilicportion of the molecule which confers solubility in the oil, is normallya polyisobutylene group. Many examples of this type of dispersant arewell known commercially and in the literature. Exemplary U.S. patentsdescribing such dispersants are U.S. Pat. Nos. 3,172,892; 3,215,707;3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,454,607; 3,541,012;3,630,904; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersantare described in U.S. Pat. Nos. 3,036,003; 3,200,107; 3,254,025;3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,413,347; 3,697,574;3,725,277; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250;3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 5,705,458. Afurther description of dispersants may be found, for example, inEuropean Patent Application No. 471 071, to which reference is made forthis purpose.

Hydrocarbyl-substituted succinic acid and hydrocarbyl-substitutedsuccinic anhydride derivatives are useful dispersants. In particular,succinimide, succinate esters, or succinate ester amides prepared by thereaction of a hydrocarbon-substituted succinic acid compound preferablyhaving at least 50 carbon atoms in the hydrocarbon substituent, with atleast one equivalent of an alkylene amine are particularly useful.

Succinimides are formed by the condensation reaction between hydrocarbylsubstituted succinic anhydrides and amines. Molar ratios can varydepending on the polyamine. For example, the molar ratio of hydrocarbylsubstituted succinic anhydride to TEPA can vary from about 1:1 to about5:1. Representative examples are shown in U.S. Pat. Nos. 3,087,936;3,172,892; 3,219,666; 3,272,746; 3,322,670; and 3,652,616, 3,948,800;and Canada Patent No. 1,094,044.

Succinate esters are formed by the condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alcohols or polyols.Molar ratios can vary depending on the alcohol or polyol used. Forexample, the condensation product of a hydrocarbyl substituted succinicanhydride and pentaerythritol is a useful dispersant.

Succinate ester amides are formed by condensation reaction betweenhydrocarbyl substituted succinic anhydrides and alkanol amines. Forexample, suitable alkanol amines include ethoxylatedpolyalkylpolyamines, propoxylated polyalkylpolyamines andpolyalkenylpolyamines such as polyethylene polyamines. One example ispropoxylated hexamethylenediamine. Representative examples are shown inU.S. Pat. No. 4,426,305.

The molecular weight of the hydrocarbyl substituted succinic anhydridesused in the preceding paragraphs will typically range between 800 and2,500 or more. The above products can be post-reacted with variousreagents such as sulfur, oxygen, formaldehyde, carboxylic acids such asoleic acid. The above products can also be post reacted with boroncompounds such as boric acid, borate esters or highly borateddispersants, to form borated dispersants generally having from about 0.1to about 5 moles of boron per mole of dispersant reaction product.

Mannich base dispersants are made from the reaction of alkylphenols,formaldehyde, and amines. See U.S. Pat. No. 4,767,551, which isincorporated herein by reference. Process aids and catalysts, such asoleic acid and sulfonic acids, can also be part of the reaction mixture.Molecular weights of the alkylphenols range from 800 to 2,500.Representative examples are shown in U.S. Pat. Nos. 3,697,574;3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,798,165; and 3,803,039.

Typical high molecular weight aliphatic acid modified Mannichcondensation products useful in this disclosure can be prepared fromhigh molecular weight alkyl-substituted hydroxyaromatics or HNR₂group-containing reactants.

Hydrocarbyl substituted amine ashless dispersant additives are wellknown to one skilled in the art; see, for example, U.S. Pat. Nos.3,275,554; 3,438,757; 3,565,804; 3,755,433, 3,822,209, and 5,084,197.

Preferred dispersants include borated and non-borated succinimides,including those derivatives from mono-succinimides, bis-succinimides,and/or mixtures of mono- and bis-succinimides, wherein the hydrocarbylsuccinimide is derived from a hydrocarbylene group such aspolyisobutylene having a Mn of from about 500 to about 5000, or fromabout 1000 to about 3000, or about 1000 to about 2000, or a mixture ofsuch hydrocarbylene groups, often with high terminal vinylic groups.Other preferred dispersants include succinic acid-esters and amides,alkylphenol-polyamine-coupled Mannich adducts, their capped derivatives,and other related components.

Polymethacrylate or polyacrylate derivatives are another class ofdispersants. These dispersants are typically prepared by reacting anitrogen containing monomer and a methacrylic or acrylic acid esterscontaining 5-25 carbon atoms in the ester group. Representative examplesare shown in U.S. Pat. Nos. 2,100,993, and 6,323,164. Polymethacrylateand polyacrylate dispersants are normally used as multifunctionalviscosity modifiers. The lower molecular weight versions can be used aslubricant dispersants or fuel detergents.

Illustrative preferred dispersants useful in this disclosure includethose derived from polyalkenyl-substituted mono- or dicarboxylic acid,anhydride or ester, which dispersant has a polyalkenyl moiety with anumber average molecular weight of at least 900 and from greater than1.3 to 1.7, preferably from greater than 1.3 to 1.6, most preferablyfrom greater than 1.3 to 1.5, functional groups (mono- or dicarboxylicacid producing moieties) per polyalkenyl moiety (a medium functionalitydispersant). Functionality (F) can be determined according to thefollowing formula:

F=(SAP×M_(n))/((112,200×A.I.)−(SAP×98))

wherein SAP is the saponification number (i.e., the number of milligramsof KOH consumed in the complete neutralization of the acid groups in onegram of the succinic-containing reaction product, as determinedaccording to ASTM D94); M_(n) is the number average molecular weight ofthe starting olefin polymer; and A.I. is the percent active ingredientof the succinic-containing reaction product (the remainder beingunreacted olefin polymer, succinic anhydride and diluent).

The polyalkenyl moiety of the dispersant may have a number averagemolecular weight of at least 900, suitably at least 1500, preferablybetween 1800 and 3000, such as between 2000 and 2800, more preferablyfrom about 2100 to 2500, and most preferably from about 2200 to about2400. The molecular weight of a dispersant is generally expressed interms of the molecular weight of the polyalkenyl moiety. This is becausethe precise molecular weight range of the dispersant depends on numerousparameters including the type of polymer used to derive the dispersant,the number of functional groups, and the type of nucleophilic groupemployed.

Polymer molecular weight, specifically M_(n), can be determined byvarious known techniques. One convenient method is gel permeationchromatography (GPC), which additionally provides molecular weightdistribution information (see W. W. Yau, J. J. Kirkland and D. D. Bly,“Modern Size Exclusion Liquid Chromatography”, John Wiley and Sons, NewYork, 1979). Another useful method for determining molecular weight,particularly for lower molecular weight polymers, is vapor pressureosmometry (e.g., ASTM D3592).

The polyalkenyl moiety in a dispersant preferably has a narrow molecularweight distribution (MWD), also referred to as polydispersity, asdetermined by the ratio of weight average molecular weight (M_(w)) tonumber average molecular weight (M_(n)). Polymers having a M_(w)/M_(n)of less than 2.2, preferably less than 2.0, are most desirable. Suitablepolymers have a polydispersity of from about 1.5 to 2.1, preferably fromabout 1.6 to about 1.8.

Suitable polyalkenes employed in the formation of the dispersantsinclude homopolymers, interpolymers or lower molecular weighthydrocarbons. One family of such polymers comprise polymers of ethyleneand/or at least one C₃ to C₂ alpha-olefin having the formula H₂C═CHR¹wherein R¹ is a straight or branched chain alkyl radical comprising 1 to26 carbon atoms and wherein the polymer contains carbon-to-carbonunsaturation, and a high degree of terminal ethenylidene unsaturation.Preferably, such polymers comprise interpolymers of ethylene and atleast one alpha-olefin of the above formula, wherein R¹ is alkyl of from1 to 18 carbon atoms, and more preferably is alkyl of from 1 to 8 carbonatoms, and more preferably still of from 1 to 2 carbon atoms.

Another useful class of polymers is polymers prepared by cationicpolymerization of monomers such as isobutene and styrene. Commonpolymers from this class include polyisobutenes obtained bypolymerization of a C₄ refinery stream having a butene content of 35 to75% by wt., and an isobutene content of 30 to 60% by wt. A preferredsource of monomer for making poly-n-butenes is petroleum feed streamssuch as Raffinate II. These feed stocks are disclosed in the art such asin U.S. Pat. No. 4,952,739. A preferred embodiment utilizespolyisobutylene prepared from a pure isobutylene stream or a Raffinate Istream to prepare reactive isobutylene polymers with terminal vinylideneolefins. Polyisobutene polymers that may be employed are generally basedon a polymer chain of from 1500 to 3000.

The dispersant(s) are preferably non-polymeric (e.g., mono- orbis-succinimides). Such dispersants can be prepared by conventionalprocesses such as disclosed in U.S. Patent Application Publication No.2008/0020950, the disclosure of which is incorporated herein byreference.

The dispersant(s) can be borated by conventional means, as generallydisclosed in U.S. Pat. Nos. 3,087,936, 3,254,025 and 5,430,105.

Such dispersants may be used in an amount of about 0.01 to 20 weightpercent or 0.01 to 10 weight percent, preferably about 0.5 to 8 weightpercent, or more preferably 0.5 to 4 weight percent. Or such dispersantsmay be used in an amount of about 2 to 12 weight percent, preferablyabout 4 to 10 weight percent, or more preferably 6 to 9 weight percent.On an active ingredient basis, such additives may be used in an amountof about 0.06 to 14 weight percent, preferably about 0.3 to 6 weightpercent. The hydrocarbon portion of the dispersant atoms can range fromC₆₀ to C₁₀₀₀, or from C₇₀ to C₃₀₀, or from C₇₀ to C₂₀₀. Thesedispersants may contain both neutral and basic nitrogen, and mixtures ofboth. Dispersants can be end-capped by borates and/or cyclic carbonates.Nitrogen content in the finished oil can vary from about 200 ppm byweight to about 2000 ppm by weight, preferably from about 200 ppm byweight to about 1200 ppm by weight. Basic nitrogen can vary from about100 ppm by weight to about 1000 ppm by weight, preferably from about 100ppm by weight to about 600 ppm by weight.

Dispersants as described herein are beneficially useful with thecompositions of this disclosure and substitute for some or all of thesurfactants of this disclosure. Further, in one embodiment, preparationof the compositions of this disclosure using one or more dispersants isachieved by combining ingredients of this disclosure, plus optional basestocks and lubricant additives, in a mixture at a temperature above themelting point of such ingredients, particularly that of the one or moreM-carboxylates (M=H, metal, two or more metals, mixtures thereof).

As used herein, the dispersant concentrations are given on an “asdelivered” basis. Typically, the active dispersant is delivered with aprocess oil. The “as delivered” dispersant typically contains from about20 weight percent to about 80 weight percent, or from about 40 weightpercent to about 60 weight percent, of active dispersant in the “asdelivered” dispersant product.

Detergents

Illustrative detergents useful in this disclosure include, for example,alkali metal detergents, alkaline earth metal detergents, or mixtures ofone or more alkali metal detergents and one or more alkaline earth metaldetergents. A typical detergent is an anionic material that contains along chain hydrophobic portion of the molecule and a smaller anionic oroleophobic hydrophilic portion of the molecule. The anionic portion ofthe detergent is typically derived from an organic acid such as asulfur-containing acid, carboxylic acid (e.g., salicylic acid),phosphorus-containing acid, phenol, or mixtures thereof. The counterionis typically an alkaline earth or alkali metal. The detergent can beoverbased as described herein.

The detergent is preferably a metal salt of an organic or inorganicacid, a metal salt of a phenol, or mixtures thereof. The metal ispreferably selected from an alkali metal, an alkaline earth metal, andmixtures thereof. The organic or inorganic acid is selected from analiphatic organic or inorganic acid, a cycloaliphatic organic orinorganic acid, an aromatic organic or inorganic acid, and mixturesthereof.

The metal is preferably selected from an alkali metal, an alkaline earthmetal, and mixtures thereof. More preferably, the metal is selected fromcalcium (Ca), magnesium (Mg), and mixtures thereof.

The organic acid or inorganic acid is preferably selected from asulfur-containing acid, a carboxylic acid, a phosphorus-containing acid,and mixtures thereof.

Preferably, the metal salt of an organic or inorganic acid or the metalsalt of a phenol comprises calcium phenate, calcium sulfonate, calciumsalicylate, magnesium phenate, magnesium sulfonate, magnesiumsalicylate, an overbased detergent, and mixtures thereof.

Salts that contain a substantially stochiometric amount of the metal aredescribed as neutral salts and have a total base number (TBN, asmeasured by ASTM D2896) of from 0 to 80. Many compositions areoverbased, containing large amounts of a metal base that is achieved byreacting an excess of a metal compound (a metal hydroxide or oxide, forexample) with an acidic gas (such as carbon dioxide). Useful detergentscan be neutral, mildly overbased, or highly overbased. These detergentscan be used in mixtures of neutral, overbased, highly overbased calciumsalicylate, sulfonates, phenates and/or magnesium salicylate,sulfonates, phenates. The TBN ranges can vary from low, medium to highTBN products, including as low as 0 to as high as 600. Preferably theTBN delivered by the detergent is between 1 and 20. More preferablybetween 1 and 12. Mixtures of low, medium, high TBN can be used, alongwith mixtures of calcium and magnesium metal based detergents, andincluding sulfonates, phenates, salicylates, and carboxylates. Adetergent mixture with a metal ratio of 1, in conjunction of a detergentwith a metal ratio of 2, and as high as a detergent with a metal ratioof 5, can be used. Borated detergents can also be used.

Alkaline earth phenates are another useful class of detergent. Thesedetergents can be made by reacting alkaline earth metal hydroxide oroxide (CaO, Ca(OH)₂, BaO, Ba(OH)₂, MgO, Mg(OH)₂, for example) with analkyl phenol or sulfurized alkylphenol. Useful alkyl groups includestraight chain or branched C₁-C₃₀ alkyl groups, preferably, C₄-C₂₀ ormixtures thereof. Examples of suitable phenols include isobutylphenol,2-ethylhexylphenol, nonylphenol, dodecyl phenol, and the like. It shouldbe noted that starting alkylphenols may contain more than one alkylsubstituent that are each independently straight chain or branched andcan be used from 0.5 to 6 weight percent. When a non-sulfurizedalkylphenol is used, the sulfurized product may be obtained by methodswell known in the art. These methods include heating a mixture ofalkylphenol and sulfurizing agent (including elemental sulfur, sulfurhalides such as sulfur dichloride, and the like) and then reacting thesulfurized phenol with an alkaline earth metal base.

In accordance with this disclosure, metal salts of carboxylic acids arepreferred detergents. These carboxylic acid detergents may be preparedby reacting a basic metal compound with at least one carboxylic acid andremoving free water from the reaction product. These compounds may beoverbased to produce the desired TBN level. Detergents made fromsalicylic acid are one preferred class of detergents derived fromcarboxylic acids. Useful salicylates include long chain alkylsalicylates. One useful family of compositions is of the formula

where R is an alkyl group having 1 to about 30 carbon atoms, n is aninteger from 1 to 4, and M is an alkaline earth metal. Preferred Rgroups are alkyl chains of at least C₁₁, preferably C₁₃ or greater. Rmay be optionally substituted with substituents that do not interferewith the detergent's function. M is preferably, calcium, magnesium,barium, or mixtures thereof. More preferably, M is calcium.

Hydrocarbyl-substituted salicylic acids may be prepared from phenols bythe Kolbe reaction (see U.S. Pat. No. 3,595,791). The metal salts of thehydrocarbyl-substituted salicylic acids may be prepared by doubledecomposition of a metal salt in a polar solvent such as water oralcohol.

Alkaline earth metal phosphates are also used as detergents and areknown in the art.

Detergents may be simple detergents or what is known as hybrid orcomplex detergents. The latter detergents can provide the properties oftwo detergents without the need to blend separate materials. See U.S.Pat. No. 6,034,039.

Preferred detergents include calcium sulfonates, magnesium sulfonates,calcium salicylates, magnesium salicylates, calcium phenates, magnesiumphenates, and other related components (including borated detergents),and mixtures thereof. Preferred mixtures of detergents include magnesiumsulfonate and calcium salicylate, magnesium sulfonate and calciumsulfonate, magnesium sulfonate and calcium phenate, calcium phenate andcalcium salicylate, calcium phenate and calcium sulfonate, calciumphenate and magnesium salicylate, calcium phenate and magnesium phenate.Overbased detergents are also preferred.

The detergent concentration in the lubricating oils of this disclosurecan range from about 0.5 to about 6.0 weight percent, preferably about0.6 to 5.0 weight percent, and more preferably from about 0.8 weightpercent to about 4.0 weight percent, based on the total weight of thelubricating oil.

As used herein, the detergent concentrations are given on an “asdelivered” basis. Typically, the active detergent is delivered with aprocess oil. The “as delivered” detergent typically contains from about20 weight percent to about 100 weight percent, or from about 40 weightpercent to about 60 weight percent, of active detergent in the “asdelivered” detergent product.

Other Antioxidants

Other antioxidants may be used in combination with the monomeric,oligomeric and polymeric aminic antioxidants. Antioxidants retard theoxidative degradation of base oils during service. Such degradation mayresult in deposits on metal surfaces, the presence of sludge, or aviscosity increase in the lubricant. One skilled in the art knows a widevariety of oxidation inhibitors that are useful in lubricating oilcompositions. See, Klamann in Lubricants and Related Products, op cite,and U.S. Pat. Nos. 4,798,684 and 5,084,197, for example.

Useful antioxidants include amine antioxidants, preferably aromaticamine antioxidants. Other useful antioxidants include phenolicantioxidants (e.g., hindered phenolic antioxidants). Aromatic amineantioxidants may be used alone or in combination with phenolicantioxidants. Typical examples of amine antioxidants include: alkylatedand non-alkylated aromatic amines such as aromatic monoamines of theformula R⁸R⁹R¹⁰N where R⁸ is an aliphatic, aromatic or substitutedaromatic group, R⁹ is an aromatic or a substituted aromatic group, andR¹⁰ is H, alkyl, aryl or R¹¹S(O)xR¹² where R¹¹ is an alkylene,alkenylene, or aralkylene group, R¹² is a higher alkyl group, or analkenyl, aryl, or alkaryl group, and x is 0, 1 or 2. The aliphatic groupR⁸ may contain from 1 to 20 carbon atoms, and preferably contains from 6to 12 carbon atoms. The aliphatic group is an aliphatic group.Preferably, both R⁸ and R⁹ are aromatic or substituted aromatic groups,and the aromatic group may be a fused ring aromatic group such asnaphthyl. Aromatic groups R⁸ and R⁹ may be joined together with othergroups such as S.

Typical aromatic amine antioxidants have alkyl substituent groups of atleast 6 carbon atoms. Examples of aliphatic groups include hexyl,heptyl, octyl, nonyl, and decyl. Generally, the aliphatic groups willnot contain more than 14 carbon atoms. The general types of amineantioxidants useful in the present compositions include diphenylamines,phenyl naphthylamines, phenothiazines, imidodibenzyls and diphenylphenylene diamines. Mixtures of two or more aromatic amines are alsouseful. Particular examples of aromatic amine antioxidants useful in thepresent disclosure include: p,p′-dioctyldiphenylamine;t-octylphenyl-alpha-naphthylamine; phenyl-alpha-naphthylamine; andp-octylphenyl-alpha-naphthylamine.

The arylamines antioxidants may be used individually or in combination.Such additives may be used in an amount of 0.01 to 5 weight percent,preferably 0.01 to 1.5 weight percent, more preferably zero to less than1.5 weight percent, more preferably zero to less than 1 weight percent.

The phenolic antioxidants may be used individually or in combination.The phenolic antioxidants may provide potential benefits in otherperformance aspects. Such additives may be used in an amount of 0.01 to1 weight percent, preferably 0.01 to 0.75 weight percent, morepreferably zero to less than 0.5 weight percent.

Viscosity Modifiers

Viscosity modifiers (also known as viscosity index improvers (VIimprovers), and viscosity improvers) can be included in the lubricantcompositions of this disclosure.

Viscosity modifiers provide lubricants with high and low temperatureoperability. These additives impart shear stability at elevatedtemperatures and acceptable viscosity at low temperatures.

Suitable viscosity modifiers include high molecular weight hydrocarbons,polyesters and viscosity modifier dispersants that function as both aviscosity modifier and a dispersant. Typical molecular weights of thesepolymers are between about 10,000 to 1,500,000, more typically about20,000 to 1,200,000, and even more typically between about 50,000 and1,000,000.

Examples of suitable viscosity modifiers are linear or star-shapedpolymers and copolymers of methacrylate, butadiene, olefins, oralkylated styrenes. Polyisobutylene is a commonly used viscositymodifier. Another suitable viscosity modifier is polymethacrylate(copolymers of various chain length alkyl methacrylates, for example),some formulations of which also serve as pour point depressants. Othersuitable viscosity modifiers include copolymers of ethylene andpropylene, hydrogenated block copolymers of styrene and isoprene, andpolyacrylates (copolymers of various chain length acrylates, forexample). Specific examples include styrene-isoprene orstyrene-butadiene based polymers of 50,000 to 200,000 molecular weight.

Olefin copolymers are commercially available from Chevron OroniteCompany LLC under the trade designation “PARATONE®” (such as “PARATONE®8921” and “PARATONE® 8941”); from Afton Chemical Corporation under thetrade designation “HiTEC®” (such as “HiTEC® 5850B”; and from TheLubrizol Corporation under the trade designation “Lubrizol® 7067C”.Hydrogenated polyisoprene star polymers are commercially available fromInfineum International Limited, e.g., under the trade designation“SV200” and “SV600”. Hydrogenated diene-styrene block copolymers arecommercially available from Infineum International Limited, e.g., underthe trade designation “SV 50”.

The polymethacrylate or polyacrylate polymers can be linear polymerswhich are available from Evnoik Industries under the trade designation“Viscoplex®” (e.g., Viscoplex 6-954) or star polymers which areavailable from Lubrizol Corporation under the trade designation Asteric™(e.g., Lubrizol 87708 and Lubrizol 87725).

Illustrative vinyl aromatic-containing polymers useful in thisdisclosure may be derived predominantly from vinyl aromatic hydrocarbonmonomer. Illustrative vinyl aromatic-containing copolymers useful inthis disclosure may be represented by the following general formula:

A-B

wherein A is a polymeric block derived predominantly from vinyl aromatichydrocarbon monomer, and B is a polymeric block derived predominantlyfrom conjugated diene monomer.

In an embodiment of this disclosure, the viscosity modifiers may be usedin an amount of less than about 10 weight percent, preferably less thanabout 7 weight percent, more preferably less than about 4 weightpercent, and in certain instances, may be used at less than 2 weightpercent, preferably less than about 1 weight percent, and morepreferably less than about 0.5 weight percent, based on the total weightof the formulated oil or lubricating engine oil. Viscosity modifiers aretypically added as concentrates, in large amounts of diluent oil.

As used herein, the viscosity modifier concentrations are given on an“as delivered” basis. Typically, the active polymer is delivered with adiluent oil. The “as delivered” viscosity modifier typically containsfrom 20 weight percent to 75 weight percent of an active polymer forpolymethacrylate or polyacrylate polymers, or from 8 weight percent to20 weight percent of an active polymer for olefin copolymers,hydrogenated polyisoprene star polymers, or hydrogenated diene-styreneblock copolymers, in the “as delivered” polymer concentrate.

Pour Point Depressants (PPDs)

Conventional pour point depressants (also known as lube oil flowimprovers) may be added to the compositions of the present disclosure ifdesired. These pour point depressant may be added to lubricatingcompositions of the present disclosure to lower the minimum temperatureat which the fluid will flow or can be poured. Examples of suitable pourpoint depressants include polymethacrylates, polyacrylates,polyarylamides, condensation products of haloparaffin waxes and aromaticcompounds, vinyl carboxylate polymers, and terpolymers ofdialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.U.S. Pat. Nos. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,655, 479;2,666,746; 2,721,877; 2,721,878; and 3,250,715 describe useful pourpoint depressants and/or the preparation thereof. Such additives may beused in an amount of about 0.01 to 5 weight percent, preferably about0.01 to 1.5 weight percent.

Seal Compatibility Agents

Seal compatibility agents help to swell elastomeric seals by causing achemical reaction in the fluid or physical change in the elastomer.Suitable seal compatibility agents for lubricating oils include organicphosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzylphthalate, for example), and polybutenyl succinic anhydride. Suchadditives may be used in an amount of about 0.01 to 3 weight percent,preferably about 0.01 to 2 weight percent.

Antifoam Agents

Anti-foam agents may advantageously be added to lubricant compositions.These agents retard the formation of stable foams. Silicones and organicpolymers are typical anti-foam agents. For example, polysiloxanes, suchas silicon oil or polydimethyl siloxane, provide antifoam properties.Anti-foam agents are commercially available and may be used inconventional minor amounts along with other additives such asdemulsifiers; usually the amount of these additives combined is lessthan 1 weight percent and often less than 0.1 weight percent.

Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protectlubricated metal surfaces against chemical attack by water or othercontaminants. A wide variety of these are commercially available.

One type of antirust additive is a polar compound that wets the metalsurface preferentially, protecting it with a film of oil. Another typeof antirust additive absorbs water by incorporating it in a water-in-oilemulsion so that only the oil touches the metal surface. Yet anothertype of antirust additive chemically adheres to the metal to produce anon-reactive surface. Examples of suitable additives include zincdithiophosphates, metal phenolates, basic metal sulfonates, fatty acidsand amines. Such additives may be used in an amount of about 0.01 to 5weight percent, preferably about 0.01 to 1.5 weight percent.

Friction Modifiers

A friction modifier is any material or materials that can alter thecoefficient of friction of a surface lubricated by any lubricant orfluid containing such material(s). Friction modifiers, also known asfriction reducers, or lubricity agents or oiliness agents, and othersuch agents that change the ability of base oils, formulated lubricantcompositions, or functional fluids, to modify the coefficient offriction of a lubricated surface may be effectively used in combinationwith the base oils or lubricant compositions of the present disclosureif desired. Friction modifiers that lower the coefficient of frictionare particularly advantageous in combination with the base oils and lubecompositions of this disclosure.

Illustrative friction modifiers may include, for example, organometalliccompounds or materials, or mixtures thereof. Illustrative organometallicfriction modifiers useful in the lubricating engine oil formulations ofthis disclosure include, for example, molybdenum amine, molybdenumdiamine, an organotungstenate, a molybdenum dithiocarbamate, molybdenumdithiophosphates, molybdenum amine complexes, molybdenum carboxylates,and the like, and mixtures thereof. Similar tungsten based compounds maybe preferable.

Other illustrative friction modifiers useful in the lubricating engineoil formulations of this disclosure include, for example, alkoxylatedfatty acid esters, alkanolamides, polyol fatty acid esters, boratedglycerol fatty acid esters, fatty alcohol ethers, and mixtures thereof.

Illustrative alkoxylated fatty acid esters include, for example,polyoxyethylene stearate, fatty acid polyglycol ester, and the like.These can include polyoxypropylene stearate, polyoxybutylene stearate,polyoxyethylene isosterate, polyoxypropylene isostearate,polyoxyethylene palmitate, and the like.

Illustrative alkanolamides include, for example, lauric aciddiethylalkanolamide, palmic acid diethylalkanolamide, and the like.These can include oleic acid diethyalkanolamide, stearic aciddiethylalkanolamide, oleic acid diethylalkanolamide, polyethoxylatedhydrocarbylamides, polypropoxylated hydrocarbylamides, and the like.

Illustrative polyol fatty acid esters include, for example, glycerolmono-oleate, saturated mono-, di-, and tri-glyceride esters, glycerolmono-stearate, and the like. These can include polyol esters,hydroxyl-containing polyol esters, and the like.

Illustrative borated glycerol fatty acid esters include, for example,borated glycerol mono-oleate, borated saturated mono-, di-, andtri-glyceride esters, borated glycerol mono-sterate, and the like. Inaddition to glycerol polyols, these can include trimethylolpropane,pentaerythritol, sorbitan, and the like. These esters can be polyolmonocarboxylate esters, polyol dicarboxylate esters, and on occasionpolyoltricarboxylate esters. Preferred can be the glycerol mono-oleates,glycerol dioleates, glycerol trioleates, glycerol monostearates,glycerol distearates, and glycerol tristearates and the correspondingglycerol monopalmitates, glycerol dipalmitates, and glyceroltripalmitates, and the respective isostearates, linoleates, and thelike. On occasion the glycerol esters can be preferred as well asmixtures containing any of these. Ethoxylated, propoxylated, butoxylatedfatty acid esters of polyols, especially using glycerol as underlyingpolyol can be preferred.

Illustrative fatty alcohol ethers include, for example, stearyl ether,myristyl ether, and the like. Alcohols, including those that have carbonnumbers from C₃ to C₅₀, can be ethoxylated, propoxylated, or butoxylatedto form the corresponding fatty alkyl ethers. The underlying alcoholportion can preferably be stearyl, myristyl, C₁₁-C₁₃ hydrocarbon, oleyl,isosteryl, and the like.

The lubricating oils of this disclosure exhibit desired properties,e.g., wear control, in the presence or absence of a friction modifier.

Useful concentrations of friction modifiers may range from 0.01 weightpercent to 5 weight percent, or about 0.1 weight percent to about 2.5weight percent, or about 0.1 weight percent to about 1.5 weight percent,or about 0.1 weight percent to about 1 weight percent. Concentrations toof molybdenum-containing materials are often described in terms of Mometal concentration.

Advantageous concentrations of Mo may range from 25 ppm to 700 ppm ormore, and often with a preferred range of 50-200 ppm. Friction modifiersof all types may be used alone or in mixtures with the materials of thisdisclosure. Often mixtures of two or more friction modifiers, ormixtures of friction modifier(s) with alternate surface activematerial(s), are also desirable.

Antiwear Additives

A metal alkylthiophosphate and more particularly a metal dialkyl dithiophosphate in which the metal constituent is zinc, or zinc dialkyl dithiophosphate (ZDDP) can be a useful component of the lubricating oils ofthis disclosure. ZDDP can be derived from primary alcohols, secondaryalcohols or mixtures thereof. ZDDP compounds generally are of theformula

Zn[SP(S)(OR¹)(OR²)]₂

where R¹ and R² are C₁-C₁₈ alkyl groups, preferably C₂-C₁₂ alkyl groups.These alkyl groups may be straight chain or branched. Alcohols used inthe ZDDP can be propanol, 2-propanol, butanol, secondary butanol,pentanols, hexanols such as 4-methyl-2-pentanol, n-hexanol, n-octanol,2-ethyl hexanol, alkylated phenols, and the like. Mixtures of secondaryalcohols or of primary and secondary alcohol can be preferred. Alkylaryl groups may also be used.

Preferable zinc dithiophosphates which are commercially availableinclude secondary zinc dithiophosphates such as those available from forexample, The Lubrizol Corporation under the trade designations “LZ677A”, “LZ 1095” and “LZ 1371”, from for example Chevron Oronite underthe trade designation “OLOA 262” and from for example Afton Chemicalunder the trade designation “HITEC 7169”.

The ZDDP is typically used in amounts of from about 0.3 weight percentto about 1.5 weight percent, preferably from about 0.4 weight percent toabout 1.2 weight percent, more preferably from about 0.5 weight percentto about 1.0 weight percent, and even more preferably from about 0.6weight percent to about 0.8 weight percent, based on the total weight ofthe lubricating oil, although more or less can often be usedadvantageously. Preferably, the ZDDP is a secondary ZDDP and present inan amount of from about 0.6 to 1.0 weight percent of the total weight ofthe lubricating oil.

The types and quantities of performance additives used in combinationwith the instant disclosure in lubricant compositions are not limited bythe examples shown herein as illustrations.

When lubricating oil compositions contain one or more of the additivesdiscussed above, the additive(s) are blended into the composition in anamount sufficient for it to perform its intended function. Typicalamounts of such additives useful in the present disclosure are shown inTable 1 below.

It is noted that many of the additives are shipped from the additivemanufacturer as a concentrate, containing one or more additivestogether, with a certain amount of base oil diluents. Accordingly, theweight amounts in the table below, as well as other amounts mentionedherein, are directed to the amount of active ingredient (that is thenon-diluent portion of the ingredient). The weight percent (wt %)indicated below is based on the total weight of the lubricating oilcomposition.

TABLE 1 Typical Amounts of Other Lubricating Oil Components ApproximateApproximate Compound wt % (Useful) wt % (Preferred) Antiwear 0.1-2 0.5-1Dispersant  0.1-20 0.1-8 Detergent  0.1-20 0.1-8 Other Antioxidant 0.1-10 0.1-5 Friction Modifier 0.01-5  0.01-1.5 Pour Point Depressant0.0-5 0.01-1.5 (PPD) Anti-foam Agent 0.001-3  0.001-0.15 Viscosity IndexImprover 0.0-8 0.1-6 (pure polymer basis) Inhibitor and Antirust 0.01-5 0.01-1.5

The foregoing additives are all commercially available materials. Theseadditives may be added independently but are usually precombined inpackages which can be obtained from suppliers of lubricant oiladditives. Additive packages with a variety of ingredients, proportionsand characteristics are available and selection of the appropriatepackage will take the requisite use of the ultimate composition intoaccount.

The following non-limiting examples are provided to illustrate thedisclosure.

EXAMPLES

Engine oil candidates were formulated. All of the ingredients used inthe candidate formulated oils were commercially available. Thenomenclature of illustrative antioxidants used in the candidateformulated oils include octylated/butylated diphenylamine (Irganox® L57from BASF Corporation) and bis(nonylphenyl)amine (Irganox® L67 from BASFCorporation).

Irganox® L57 is a mixture of several different substituted diphenylamine antioxidants. The four most common molecular weights, and therelative amounts, for the Irganox® L57 constituents are as follows:

Molecular Weight % Content Monomer A 225.34 16 Monomer B 281.44 37Monomer C 337.5 28 Monomer D 393.66 19

Oligomers from Irganox® L57 can be formed, for example, self-oligomerslike A+A, A+A+A, or C+C+C+C or mixed oligomers like A+B, A+B+C, B+A+D+Din a myriad of combinations. When the monomers of Irganox® L57oligomerize, they can form dimers, trimers and higher order oligomers invarying abundance which is in part governed by the relative abundance ofthe monomers as well as the relative reactivity of the monomer. Therelative concentration of higher order oligomers will decrease as thesize of the oligomer increases due to molecular diversity that isproduced. As such, the oligomers expected to be formed in the highestconcentration will be dimers, followed by trimers and so forth.

The candidates were fully formulated lubricants. In addition to Irganox®L57, the formulations contained typical base stocks combined withdispersants, detergents, antiwear additives, friction modifiers, and thelike.

Formulated oils including an inventive example (i.e., inventive Example2 having 5 weight percent Irganox® L57) and a comparative example (i.e.,comparative Example 1 having 0.75 weight percent Irganox® L57) weretested according to a Sequence IIIH engine test until % viscosityincrease exceeded 100%. The monomeric aminic antioxidants were eachadded to an engine oil at the indicated concentration. The Sequence IIIHTest (ASTM D8111) is a fired-engine, dynamometer lubricant test forevaluating automotive engine oils for certain high-temperatureperformance characteristics, including oil thickening, varnishdeposition and oil consumption. The Sequence IIIH engine test resultsare shown below.

Example 1 Example 2 Irganox L57 0.75 wt % 5 wt % Sequence IIIH %Viscosity increase at 150 hours 118% 52% Average Piston Varnish Merits3.75 5.6 Average Piston Deposit Merits 8.66 9.79

The inventive Example 2 provided outstanding viscosity performance whilemaintaining improved deposits performance. Lower % viscosity increase isbetter. Higher “merits” is better.

Used oil samples from the Sequence IIIH engine testing were analyzed byliquid chromatography mass spectrometry (LCMS) to quantify the relativeconcentration of molecular ions of interest. The data was then analyzedby the following equation:

[(oligomer ions at time point/total ions at time point)−(oligomer ionsat zero hours/total ions at zero hours)]×1000=relative amount ofoligomers detected by LCMS

In this way, all data was normalized prior to the start of the test.Values reported are the relative increase in the amount of thatoligomer. Values less than 1 can be considered noise in the system,while values greater than 1 represent a real increase in the amount ofan oligomer.

Ion counts for oligomers of Irganox® L57 in comparative Example 1formulated oil analyzed by LCMS are shown in FIG. 1.

Ion counts for oligomers of Irganox® L57 in inventive Example 2formulated oil analyzed by LCMS are shown in FIG. 2.

In an embodiment, a preformed oligomeric or polymeric aminic antioxidantcan be co-formulated with a monomeric aminic antioxidant. The presenceof additional monomeric aminic antioxidant starting material allows forthe oligomeric or polymeric antioxidant to form even larger oligomersand polymers and regenerate itself throughout the oil drain interval.

In particular, in addition to formulated oils containing only monomericaminic antioxidants, there can also be oils that are formulated with anoligomeric aminic antioxidant (such as MCP 2568, Nycoperf® A0337, orVanlube® 9317) in addition to a monomeric aminic antioxidant (such asIrganox® L57, Irganox® L67, or Irganox® L06). In this embodiment, themonomeric aminic antioxidant can further react with the preexistingoligomeric aminic antioxidants to form various combinations of evenhigher order oligomers. This function is self-healing as the newlyattached monomers replace other portions of the preexisting oligomerthat have degraded during the lifetime of the formulated oil. Thisadditional oligomerization can also improve the antioxidancy of thepreexisting oligomers, as some higher order oligomers are more potentantioxidants than lower order oligomers.

In another embodiment, simplified formulations containing only monomericaminic antioxidant and base stock, generate in situ oligomeric andpolymeric aminic antioxidants in lubricating oil formulations.

In yet another embodiment, some consumers have a particular preferencefor oils that are not dark in color. The color of a formulated oil canbe measured using various methods, including ASTM D1500. In thisembodiment, it is sometimes preferable to have a formulated oil with acolor less than 6 according to ASTM D1500. Current available oligomericaminic antioxidants often suffer from the problem of being very dark innature. When used in a formulated oil at an appropriate treat rate,these materials can result in a final formulation color that isunacceptable to the consumer. One particular advantage of thisdisclosure is that these formulations are not dark in nature becausemonomeric aminic antioxidants tend to be much lighter in color accordingto ASTM D1500.

The lubricating oils of this disclosure can also be test in accordancewith the General Motors Oxidation and Deposit Test (GMOD) in accordancewith GMW17043, 2^(nd) Edition, May 2016. The GMOD test procedure coversengine tests for evaluating automotive engine oils for certain hightemperature performance characteristics, including oil thickening, andpiston deposits. Additionally, secondary requirements that can beconducted include mini rotary viscometer measurements, cold crankingsimulator measurements, and phosphorus retention measurements.

It has been found that, with in situ generated oligomeric and polymericaminic antioxidants in lubricating oil formulations, viscosity controland deposit control are improved in the finished formulations designedfor engine oil applications.

ADDITIONAL EMBODIMENTS Embodiment 1

A method for controlling formation and dissipation of at least oneoligomeric or polymeric aminic antioxidant in a lubricating oil, duringoperation of an engine or other mechanical component lubricated with thelubricating oil by using as the lubricating oil a formulated oil, saidformulated oil having a composition comprising a lubricating oil basestock as a major component; and at least one oligomeric or polymericaminic antioxidant, as a minor component; wherein the at least oneoligomeric or polymeric aminic antioxidant is formed over time in situfrom at least one monomeric aminic antioxidant during operation of theengine or other mechanical component; wherein the at least oneoligomeric or polymeric aminic antioxidant is dissipated over time inthe lubricating oil during operation of the engine or other mechanicalcomponent; wherein the lubricating oil base stock is present in anamount from about 1 to about 95 weight percent, based on the totalweight of the lubricating oil; and wherein the at least one monomericaminic antioxidant is present in an amount from greater than about 2 toabout 10 weight percent, based on the total weight of the lubricatingoil.

Embodiment 2

The method of claim 1 wherein, in measurements of the lubricating oil bya Sequence IIIH engine test in accordance with ASTM D8111-17, viscositycontrol and deposit control are improved using a concentration of the atleast one monomeric aminic antioxidant from greater than about 2 toabout 10 weight percent, based on the total weight of the lubricatingoil, as compared to viscosity control and deposit control achieved usinga lower concentration of the at least one monomeric aminic antioxidant.

Embodiment 3

The method of claim 1 wherein the at least one monomeric aminicantioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 4

The method of claim 1 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of at least one unsubstituted or hydrocarbyl-substituteddiphenyl amine, at least one unsubstituted or hydrocarbyl-substitutedphenyl naphthyl amine, or both at least one unsubstituted orhydrocarbyl-substituted diphenylamine and at least one unsubstituted orhydrocarbyl-substituted phenyl naphthylamine.

Embodiment 5

The method of claim 1 wherein the at least one oligomeric or polymericaminic antioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 6

The method of claim 1 wherein the at least one monomeric aminicantioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 7

The method of claim 1 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 8

The method of claim 7 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A),(A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.

Embodiment 9

The method of claim 7 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 10

The method of claim 1 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 11

The method of claim 1 wherein the lubricating oil base stock is presentin an amount from about 1 to about 80 weight percent, based on the totalweight of the lubricating oil.

Embodiment 12

The method of claim 1 wherein the at least one monomeric aminicantioxidant is present in an amount from about 4 to about 8 weightpercent, based on the total weight of the lubricating oil.

Embodiment 13

The method of claim 1 wherein the at least one oligomeric or polymericaminic antioxidant is present in an amount from about 0.1 to about 5weight percent, based on the total weight of the lubricating oil.

Embodiment 14

The method of claim 1 wherein the formulated oil further comprises oneor more of a viscosity modifier, dispersant, detergent, otherantioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 15

The method of claim 14 wherein the other antioxidant comprises at leastone aromatic amine antioxidant, at least one phenolic antioxidant, ormixtures thereof.

Embodiment 16

The method of claim 1 wherein the at least one oligomeric or polymericaminic antioxidant is formed over time in situ during a Sequence IIIHengine test in accordance with ASTM D8111-17, or a General MotorsOxidation and Deposit Test (GMOD) in accordance with GMW17043, 2^(nd)Edition, May 2016.

Embodiment 17

The method of claim 1 wherein the lubricating oil is a passenger vehicleengine oil (PVEO), a commercial vehicle engine oil (CVEO), or alubricating oil that is subjected to heat and oxidative conditions.

Embodiment 18

A method for controlling formation and dissipation of at least oneoligomeric or polymeric aminic antioxidant in a lubricating oil, duringoperation of an engine or other mechanical component lubricated with thelubricating oil by using as the lubricating oil a formulated oil, saidformulated oil having a composition comprising a lubricating oil basestock as a major component; and at least one monomeric aminicantioxidant, as a minor component; wherein at least one oligomeric orpolymeric aminic antioxidant is formed over time in situ from the atleast one monomeric aminic antioxidant during operation of the engine orother mechanical component; wherein the at least one oligomeric orpolymeric aminic antioxidant is dissipated over time in the lubricatingoil during operation of the engine or other mechanical component;wherein the lubricating oil base stock is present in an amount fromabout 1 to about 95 weight percent, based on the total weight of thelubricating oil; and wherein the at least one monomeric aminicantioxidant is present in an amount from greater than about 2 to about10 weight percent, based on the total weight of the lubricating oil.

Embodiment 19

The method of claim 18 wherein, in measurements of the lubricating oilby a Sequence IIIH engine test in accordance with ASTM D8111-17,viscosity control and deposit control are improved using a concentrationof the at least one monomeric aminic antioxidant from greater than about2 to about 10 weight percent, based on the total weight of thelubricating oil, as compared to viscosity control and deposit controlachieved using a lower concentration of the at least one monomericaminic antioxidant.

Embodiment 20

The method of claim 18 wherein the at least one monomeric aminicantioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 21

The method of claim 18 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of at least one unsubstituted or hydrocarbyl-substituteddiphenyl amine, at least one unsubstituted or hydrocarbyl-substitutedphenyl naphthyl amine, or both at least one unsubstituted orhydrocarbyl-substituted diphenylamine and at least one unsubstituted orhydrocarbyl-substituted phenyl naphthylamine.

Embodiment 22

The method of claim 18 wherein the at least one oligomeric or polymericaminic antioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 23

The method of claim 18 wherein the at least one monomeric aminicantioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 24

The method of claim 18 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 25

The method of claim 24 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A),(A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.

Embodiment 26

The method of claim 24 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 27

The method of claim 18 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 28

The method of claim 18 wherein the lubricating oil base stock is presentin an amount from about 1 to about 80 weight percent, based on the totalweight of the lubricating oil.

Embodiment 29

The method of claim 18 wherein the at least one monomeric aminicantioxidant is present in an amount from about 4 to about 8 weightpercent, based on the total weight of the lubricating oil.

Embodiment 30

The method of claim 18 wherein the at least one oligomeric or polymericaminic antioxidant is present in an amount from about 0.1 to about 5weight percent, based on the total weight of the lubricating oil.

Embodiment 31

The method of claim 18 wherein the formulated oil further comprises oneor more of a viscosity modifier, dispersant, detergent, otherantioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 32

The method of claim 31 wherein the other antioxidant comprises at leastone aromatic amine antioxidant, at least one phenolic antioxidant, ormixtures thereof.

Embodiment 33

The method of claim 18 wherein the at least one oligomeric or polymericaminic antioxidant is formed over time in situ during a Sequence IIIHengine test in accordance with ASTM D8111-17, or a General MotorsOxidation and Deposit Test (GMOD) in accordance with GMW17043, 2^(nd)Edition, May 2016.

Embodiment 34

The method of claim 18 wherein the lubricating oil is a passengervehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or alubricating oil that is subjected to heat and oxidative conditions.

Embodiment 35

A method for controlling formation and dissipation of at least oneoligomeric or polymeric aminic antioxidant in a lubricating oil, duringoperation of an engine or other mechanical component lubricated with thelubricating oil by using as the lubricating oil a formulated oil, saidformulated oil having a composition comprising a lubricating oil basestock as a major component; and at least one oligomeric or polymericaminic antioxidant and at least one monomeric aminic antioxidant, asminor components; wherein the at least one oligomeric or polymericaminic antioxidant and the at least one monomeric aminic antioxidantreact to form over time in situ at least one oligomeric or polymericaminic antioxidant reaction product during operation of the engine orother mechanical component; wherein the at least one oligomeric orpolymeric aminic antioxidant reaction product is dissipated over time inthe lubricating oil during operation of the engine or other mechanicalcomponent; wherein the lubricating oil base stock is present in anamount from about 1 to about 95 weight percent, based on the totalweight of the lubricating oil; wherein the at least one oligomeric orpolymeric aminic antioxidant is present in an amount from greater thanabout 0.1 to about 10 weight percent, based on the total weight of thelubricating oil; and wherein the at least one monomeric aminicantioxidant is present in an amount from greater than about 2 to about10 weight percent, based on the total weight of the lubricating oil.

Embodiment 36

The method of claim 35 wherein, in measurements of the lubricating oilby a Sequence IIIH engine test in accordance with ASTM D8111-17,viscosity control and deposit control are improved using a concentrationof the at least one monomeric aminic antioxidant from greater than about2 to about 10 weight percent, based on the total weight of thelubricating oil, as compared to viscosity control and deposit controlachieved using a lower concentration of the at least one monomericaminic antioxidant.

Embodiment 37

The method of claim 35 wherein the at least one monomeric aminicantioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 38

The method of claim 35 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of at least one unsubstituted or hydrocarbyl-substituteddiphenyl amine, at least one unsubstituted or hydrocarbyl-substitutedphenyl naphthyl amine, or both at least one unsubstituted orhydrocarbyl-substituted diphenylamine and at least one unsubstituted orhydrocarbyl-substituted phenyl naphthylamine.

Embodiment 39

The method of claim 35 wherein the at least one monomeric aminicantioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 40

The method of claim 35 wherein the at least one monomeric aminicantioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 41

The method of claim 35 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 42

The method of claim 41 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A),(A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.

Embodiment 43

The method of claim 41 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 44

The method of claim 35 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 45

The method of claim 35 wherein the at least one oligomeric or polymericaminic antioxidant reaction product is the oligomerization orpolymerization reaction product of:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached; with at leastone monomeric aminic antioxidant comprising:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 46

The method of claim 35 wherein the lubricating oil base stock is presentin an amount from about 1 to about 80 weight percent, based on the totalweight of the lubricating oil.

Embodiment 47

The method of claim 35 wherein the at least one monomeric aminicantioxidant is present in an amount from about 4 to about 8 weightpercent, based on the total weight of the lubricating oil.

Embodiment 48

The method of claim 35 wherein the at least one oligomeric or polymericaminic antioxidant is present in an amount from about 1 to about 8weight percent, based on the total weight of the lubricating oil.

Embodiment 49

The method of claim 35 wherein the formulated oil further comprises oneor more of a viscosity modifier, dispersant, detergent, otherantioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 50

The method of claim 49 wherein the other antioxidant comprises at leastone aromatic amine antioxidant, at least one phenolic antioxidant, ormixtures thereof.

Embodiment 51

The method of claim 35 wherein the at least one oligomeric or polymericaminic antioxidant is formed over time in situ during a Sequence IIIHengine test in accordance with ASTM D8111-17, or a General MotorsOxidation and Deposit Test (GMOD) in accordance with GMW17043, 2^(nd)Edition, May 2016.

Embodiment 52

The method of claim 35 wherein the lubricating oil is a passengervehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or alubricating oil that is subjected to heat and oxidative conditions.

Embodiment 53

A method for regenerating at least one oligomeric or polymeric aminicantioxidant in a lubricating oil, during operation of an engine or othermechanical component lubricated with the lubricating oil by using as thelubricating oil a formulated oil, said formulated oil having acomposition comprising a lubricating oil base stock as a majorcomponent; and at least one oligomeric or polymeric aminic antioxidantand at least one monomeric aminic antioxidant, as minor components;wherein the at least one oligomeric or polymeric aminic antioxidantdissipates over time in the lubricating oil during operation of theengine or other mechanical component; wherein the at least oneoligomeric or polymeric aminic antioxidant and the at least onemonomeric aminic antioxidant react to form over time in situ at leastone regenerated oligomeric or polymeric aminic antioxidant duringoperation of the engine or other mechanical component; wherein thelubricating oil base stock is present in an amount from about 1 to about95 weight percent, based on the total weight of the lubricating oil;wherein the at least one oligomeric or polymeric aminic antioxidant ispresent in an amount from greater than about 0.1 to about 10 weightpercent, based on the total weight of the lubricating oil; and whereinthe at least one monomeric aminic antioxidant is present in an amountfrom greater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil.

Embodiment 54

The method of claim 53 wherein, in measurements of the lubricating oilby a Sequence IIIH engine test in accordance with ASTM D8111-17,viscosity control and deposit control are improved using a concentrationof the at least one monomeric aminic antioxidant from greater than about2 to about 10 weight percent, based on the total weight of thelubricating oil, as compared to viscosity control and deposit controlachieved using a lower concentration of the at least one monomericaminic antioxidant.

Embodiment 55

The method of claim 53 wherein the at least one monomeric aminicantioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 56

The method of claim 53 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of at least one unsubstituted or hydrocarbyl-substituteddiphenyl amine, at least one unsubstituted or hydrocarbyl-substitutedphenyl naphthyl amine, or both at least one unsubstituted orhydrocarbyl-substituted diphenylamine and at least one unsubstituted orhydrocarbyl-substituted phenyl naphthylamine.

Embodiment 57

The method of claim 53 wherein the at least one monomeric aminicantioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 58

The method of claim 53 wherein the at least one monomeric aminicantioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 59

The method of claim 53 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 60

The method of claim 59 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A),(A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.

Embodiment 61

The method of claim 59 wherein the at least one oligomeric or polymericaminic antioxidant is the oligomerization or polymerization reactionproduct formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 62

The method of claim 53 wherein the at least one oligomeric or polymericaminic antioxidant is an oligomerization or polymerization reactionproduct selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 63

The method of claim 53 wherein the at least one regenerated oligomericor polymeric aminic antioxidant is the oligomerization or polymerizationreaction product of:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached; with at leastone monomeric aminic antioxidant comprising:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 64

The method of claim 53 wherein the lubricating oil base stock is presentin an amount from about 1 to about 80 weight percent, based on the totalweight of the lubricating oil.

Embodiment 65

The method of claim 53 wherein the at least one monomeric aminicantioxidant is present in an amount from about 4 to about 8 weightpercent, based on the total weight of the lubricating oil.

Embodiment 66

The method of claim 53 wherein the at least one oligomeric or polymericaminic antioxidant is present in an amount from about 1 to about 8weight percent, based on the total weight of the lubricating oil.

Embodiment 67

The method of claim 53 wherein the formulated oil further comprises oneor more of a viscosity modifier, dispersant, detergent, otherantioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 68

The method of claim 67 wherein the other antioxidant comprises at leastone aromatic amine antioxidant, at least one phenolic antioxidant, ormixtures thereof.

Embodiment 69

The method of claim 53 wherein the at least one oligomeric or polymericaminic antioxidant is formed over time in situ during a Sequence IIIHengine test in accordance with ASTM D8111-17, or a General MotorsOxidation and Deposit Test (GMOD) in accordance with GMW17043, 2^(nd)Edition, May 2016.

Embodiment 70

The method of claim 53 wherein the lubricating oil is a passengervehicle engine oil (PVEO), a commercial vehicle engine oil (CVEO), or alubricating oil that is subjected to heat and oxidative conditions.

Embodiment 71

A lubricating oil having a composition comprising a lubricating oil basestock as a major component, and at least one oligomeric or polymericaminic antioxidant, as a minor component; wherein, in an engine or othermechanical component lubricated with the lubricating oil, the at leastone oligomeric or polymeric aminic antioxidant is formed over time insitu from at least one monomeric aminic antioxidant during operation ofthe engine or other mechanical component; wherein the at least oneoligomeric or polymeric aminic antioxidant is dissipated over time inthe lubricating oil during operation of the engine or other mechanicalcomponent; wherein the lubricating oil base stock is present in anamount from about 1 to about 95 weight percent, based on the totalweight of the lubricating oil; and wherein the at least one monomericaminic antioxidant is present in an amount from greater than about 2 toabout 10 weight percent, based on the total weight of the lubricatingoil.

Embodiment 72

The lubricating oil of claim 71 wherein, in measurements of thelubricating oil by a Sequence IIIH engine test in accordance with ASTMD8111-17, viscosity control and deposit control are improved using aconcentration of the at least one monomeric aminic antioxidant fromgreater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil, as compared to viscosity control anddeposit control achieved using a lower concentration of the at least onemonomeric aminic antioxidant.

Embodiment 73

The lubricating oil of claim 71 wherein the at least one monomericaminic antioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 74

The lubricating oil of claim 71 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or both at least oneunsubstituted or hydrocarbyl-substituted diphenylamine and at least oneunsubstituted or hydrocarbyl-substituted phenyl naphthylamine.

Embodiment 75

The lubricating oil of claim 71 wherein the at least one monomericaminic antioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or

C1 to C30 alkyl, R³ is a styrene or C1 to C30 alkyl, q and yindividually range from 0 to up to the valence of the aryl group towhich the respective R groups are attached.

Embodiment 76

The lubricating oil of claim 71 wherein the at least one monomericaminic antioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 77

The lubricating oil of claim 71 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 78

The lubricating oil of claim 77 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B),(A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A

Embodiment 79

The lubricating oil of claim 77 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 80

The lubricating oil of claim 71 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 81

The lubricating oil of claim 71 wherein the lubricating oil base stockis present in an amount from about 1 to about 80 weight percent, basedon the total weight of the to lubricating oil.

Embodiment 82

The lubricating oil of claim 71 wherein the at least one monomericaminic antioxidant is present in an amount from about 4 to about 8weight percent, based on the total weight of the lubricating oil.

Embodiment 83

The lubricating oil of claim 71 wherein the at least one oligomeric orpolymeric aminic antioxidant is present in an amount from about 1 toabout 8 weight percent, based on the total weight of the lubricatingoil.

Embodiment 84

The lubricating oil of claim 71 wherein the formulated oil furthercomprises one or more of a viscosity modifier, dispersant, detergent,other antioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 85

The lubricating oil of claim 84 wherein the other antioxidant comprisesat least one aromatic amine antioxidant, at least one phenolicantioxidant, or mixtures thereof.

Embodiment 86

The lubricating oil of claim 71 wherein the at least one oligomeric orpolymeric aminic antioxidant is formed over time in situ during aSequence IIIH engine test in accordance with ASTM D8111-17, or a GeneralMotors Oxidation and Deposit Test (GMOD) in accordance with GMW17043,2^(nd) Edition, May 2016.

Embodiment 87

The lubricating oil of claim 71 which is a passenger vehicle engine oil(PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oilthat is subjected to heat and oxidative conditions.

Embodiment 88

A lubricating oil having a composition comprising a lubricating oil basestock as a major component, and at least one monomeric aminicantioxidant, as a minor component; wherein, in an engine or othermechanical component lubricated with the lubricating oil, at least oneoligomeric or polymeric aminic antioxidant is formed over time in situfrom the at least one monomeric aminic antioxidant during operation ofthe engine or other mechanical component; wherein the at least oneoligomeric or polymeric aminic antioxidant is dissipated over time inthe lubricating oil during operation of the engine or other mechanicalcomponent; wherein the lubricating oil base stock is present in anamount from about 1 to about 95 weight percent, based on the totalweight of the lubricating oil; and wherein the at least one monomericaminic antioxidant is present in an amount from greater than about 2 toabout 10 weight percent, based on the total weight of the lubricatingoil.

Embodiment 89

The lubricating oil of claim 88 wherein, in measurements of thelubricating oil by a Sequence IIIH engine test in accordance with ASTMD8111-17, viscosity control and deposit control are improved using aconcentration of the at least one monomeric aminic antioxidant fromgreater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil, as compared to viscosity control anddeposit control achieved using a lower concentration of the at least onemonomeric aminic antioxidant.

Embodiment 90

The lubricating oil of claim 88 wherein the at least one monomericaminic antioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 91

The lubricating oil of claim 88 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or both at least oneunsubstituted or hydrocarbyl-substituted diphenylamine and at least oneunsubstituted or hydrocarbyl-substituted phenyl naphthylamine.

Embodiment 92

The lubricating oil of claim 88 wherein the at least one monomeric toaminic antioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 93

The lubricating oil of claim 88 wherein the at least one monomericaminic antioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 94

The lubricating oil of claim 88 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 95

The lubricating oil of claim 94 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B),(A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.

Embodiment 96

The lubricating oil of claim 94 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 97

The lubricating oil of claim 88 wherein the at least one oligomeric orto polymeric aminic antioxidant is an oligomerization or polymerizationreaction product selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 98

The lubricating oil of claim 88 wherein the lubricating oil base stockis present in an amount from about 1 to about 80 weight percent, basedon the total weight of the lubricating oil.

Embodiment 99

The lubricating oil of claim 88 wherein the at least one monomericaminic antioxidant is present in an amount from about 4 to about 8weight percent, based on the total weight of the lubricating oil.

Embodiment 100

The lubricating oil of claim 88 wherein the at least one oligomeric orpolymeric aminic antioxidant is present in an amount from about 1 toabout 8 weight percent, based on the total weight of the lubricatingoil.

Embodiment 101

The lubricating oil of claim 88 wherein the formulated oil furthercomprises one or more of a viscosity modifier, dispersant, detergent,other antioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 102

The lubricating oil of claim 101 wherein the other antioxidant comprisesat least one aromatic amine antioxidant, at least one phenolicantioxidant, or mixtures thereof.

Embodiment 103

The lubricating oil of claim 88 wherein the at least one oligomeric orpolymeric aminic antioxidant is formed over time in situ during aSequence IIIH engine test in accordance with ASTM D8111-17, or a GeneralMotors Oxidation and Deposit Test (GMOD) in accordance with GMW17043,2^(nd) Edition, May 2016.

Embodiment 104

The lubricating oil of claim 88 which is a passenger vehicle engine oil(PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oilthat is subjected to heat and oxidative conditions.

Embodiment 105

A lubricating oil having a composition comprising a lubricating oil basestock as a major component, and at least one oligomeric or polymericaminic antioxidant and at least one monomeric aminic antioxidant, asminor components; wherein, in an engine or other mechanical componentlubricated with the lubricating oil, the at least one oligomeric orpolymeric aminic antioxidant and the at least one monomeric aminicantioxidant react to form over time in situ at least one oligomeric orpolymeric aminic antioxidant reaction product during operation of theengine or other mechanical component; wherein the at least oneoligomeric or polymeric aminic antioxidant reaction product isdissipated over time in the lubricating oil during operation of theengine or other mechanical component; wherein the lubricating oil basestock is present in an amount from about 1 to about 95 weight percent,based on the total weight of the lubricating oil; wherein the at leastone oligomeric or polymeric aminic antioxidant is present in an amountfrom greater than about 0.1 to about 10 weight percent, based on thetotal weight of the lubricating oil; and wherein the at least onemonomeric aminic antioxidant is present in an amount from greater thanabout 2 to about 10 weight percent, based on the total weight of thelubricating oil.

Embodiment 106

The lubricating oil of claim 105 wherein, in measurements of thelubricating oil by a Sequence IIIH engine test in accordance with ASTMD8111-17, viscosity control and deposit control are improved using aconcentration of the at least one monomeric aminic antioxidant fromgreater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil, as compared to viscosity control anddeposit control achieved using a lower concentration of the at least onemonomeric aminic antioxidant.

Embodiment 107

The lubricating oil of claim 105 wherein the at least one monomericaminic antioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 108

The lubricating oil of claim 105 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or both at least oneunsubstituted or hydrocarbyl-substituted diphenylamine and at least oneunsubstituted or hydrocarbyl-substituted phenyl naphthylamine.

Embodiment 109

The lubricating oil of claim 105 wherein the at least one monomericaminic antioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or

C1 to C30 alkyl, R³ is a styrene or C1 to C30 alkyl, q and yindividually range from 0 to up to the valence of the aryl group towhich the respective R groups are attached.

Embodiment 110

The lubricating oil of claim 105 wherein the at least one monomericaminic antioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 111

The lubricating oil of claim 105 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 112

The lubricating oil of claim 111 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B),(A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.

Embodiment 113

The lubricating oil of claim 111 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 114

The lubricating oil of claim 105 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 115

The method of claim 105 wherein the at least one oligomeric or polymericaminic antioxidant reaction product is the oligomerization orpolymerization reaction product of:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached; with at leastone monomeric aminic antioxidant comprising:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 116

The lubricating oil of claim 105 wherein the lubricating oil base stockis present in an amount from about 1 to about 80 weight percent, basedon the total weight of the lubricating oil.

Embodiment 117

The lubricating oil of claim 105 wherein the at least one monomericaminic antioxidant is present in an amount from about 4 to about 8weight percent, based on the total weight of the lubricating oil.

Embodiment 118

The lubricating oil of claim 105 wherein the at least one oligomeric orpolymeric aminic antioxidant is present in an amount from about 1 toabout 8 weight percent, based on the total weight of the lubricatingoil.

Embodiment 119

The lubricating oil of claim 105 wherein the formulated oil furthercomprises one or more of a viscosity modifier, dispersant, detergent,other antioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 120

The lubricating oil of claim 119 wherein the other antioxidant comprisesat least one aromatic amine antioxidant, at least one phenolicantioxidant, or mixtures thereof.

Embodiment 121

The lubricating oil of claim 105 wherein the at least one oligomeric orpolymeric aminic antioxidant is formed over time in situ during aSequence IIIH engine test in accordance with ASTM D8111-17, or a GeneralMotors Oxidation and Deposit Test (GMOD) in accordance with GMW17043,2^(nd) Edition, May 2016.

Embodiment 122

The lubricating oil of claim 105 which is a passenger vehicle engine oil(PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oilthat is subjected to to heat and oxidative conditions.

Embodiment 123

A lubricating oil having a composition comprising a lubricating oil basestock as a major component, and at least one oligomeric or polymericaminic antioxidant and at least one monomeric aminic antioxidant, asminor components; wherein, in an engine or other mechanical componentlubricated with the lubricating oil, the at least one oligomeric orpolymeric aminic antioxidant dissipates over time in the lubricating oilduring operation of the engine or other mechanical component; whereinthe at least one oligomeric or polymeric aminic antioxidant and the atleast one monomeric aminic antioxidant react to form over time in situat least one regenerated oligomeric or polymeric aminic antioxidantduring operation of the engine or other mechanical component; whereinthe lubricating oil base stock is present in an amount from about 1 toabout 95 weight percent, based on the total weight of the lubricatingoil; wherein the at least one oligomeric or polymeric aminic antioxidantis present in an amount from greater than about 0.1 to about 10 weightpercent, based on the total weight of the lubricating oil; and whereinthe at least one monomeric aminic antioxidant is present in an amountfrom greater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil.

Embodiment 124

The lubricating oil of claim 123 wherein, in measurements of thelubricating oil by a Sequence IIIH engine test in accordance with ASTMD8111-17, viscosity control and deposit control are improved using aconcentration of the at least one monomeric aminic antioxidant fromgreater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil, as compared to viscosity control anddeposit control achieved using a lower concentration of the at least onemonomeric aminic antioxidant.

Embodiment 125

The lubricating oil of claim 123 wherein the at least one monomericaminic antioxidant comprises at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or mixtures thereof.

Embodiment 126

The lubricating oil of claim 123 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or both at least oneunsubstituted or hydrocarbyl-substituted diphenylamine and at least oneunsubstituted or hydrocarbyl-substituted phenyl naphthylamine.

Embodiment 127

The lubricating oil of claim 123 wherein the at least one monomericaminic antioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 128

The lubricating oil of claim 123 wherein the at least one monomericaminic antioxidant comprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 129

The lubricating oil of claim 123 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.

Embodiment 130

The lubricating oil of claim 129 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product comprising: (A)(A), (A)(B), (B)(B), (A)(A)(B),(A)(A)(A), (A)(B)(A), (B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B),(A)(A)(A)(B), (B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A),(A)(B)(A)(B)(A), (A)(B)(B)(B)(A), or mixtures thereof.

Embodiment 131

The lubricating oil of claim 129 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product formed by any combination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 132

The lubricating oil of claim 123 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.

Embodiment 133

The method of claim 123 wherein the at least one regenerated oligomericor polymeric aminic antioxidant is the oligomerization or polymerizationreaction product of:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached; with at leastone monomeric aminic antioxidant comprising:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or

Embodiment 134

The lubricating oil of claim 123 wherein the lubricating oil base stockis present in an amount from about 1 to about 80 weight percent, basedon the total weight of the lubricating oil.

Embodiment 135

The lubricating oil of claim 123 wherein the at least one monomericaminic antioxidant is present in an amount from about 4 to about 8weight percent, based on the total weight of the lubricating oil.

Embodiment 136

The lubricating oil of claim 123 wherein the at least one oligomeric orpolymeric aminic antioxidant is present in an amount from about 1 toabout 8 weight percent, based on the total weight of the lubricatingoil.

Embodiment 137

The lubricating oil of claim 123 wherein the formulated oil furthercomprises one or more of a viscosity modifier, dispersant, detergent,other antioxidant, pour point depressant, corrosion inhibitor, metaldeactivator, seal compatibility additive, anti-foam agent, inhibitor,and anti-rust additive.

Embodiment 138

The lubricating oil of claim 137 wherein the other antioxidant comprisesat least one aromatic amine antioxidant, at least one phenolicantioxidant, or mixtures thereof.

Embodiment 139

The lubricating oil of claim 123 wherein the at least one regeneratedoligomeric or polymeric aminic antioxidant is formed overtime in situduring a Sequence IIIH engine test in accordance with ASTM D8111-17, ora General Motors Oxidation and Deposit Test (GMOD) in accordance withGMW17043, 2^(nd) Edition, May 2016.

Embodiment 140

The lubricating oil of claim 123 which is a passenger vehicle engine oil(PVEO), a commercial vehicle engine oil (CVEO), or a lubricating oilthat is subjected to heat and oxidative conditions.

All patents and patent applications, test procedures (such as ASTMmethods, UL methods, and the like), and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this disclosure and for all jurisdictions in whichsuch incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

The present disclosure has been described above with reference tonumerous embodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims

1. A method for controlling formation and dissipation of at least oneoligomeric or polymeric aminic antioxidant in a lubricating oil, duringoperation of an engine or other mechanical component lubricated with thelubricating oil by using as the lubricating oil a formulated oil, saidformulated oil having a composition comprising a lubricating oil basestock as a major component; and at least one oligomeric or polymericaminic antioxidant, as a minor component; wherein the at least oneoligomeric or polymeric aminic antioxidant is formed over time in situfrom at least one monomeric aminic antioxidant during operation of theengine or other mechanical component; wherein the at least oneoligomeric or polymeric aminic antioxidant is dissipated over time inthe lubricating oil during operation of the engine or other mechanicalcomponent; wherein the lubricating oil base stock is present in anamount from about 1 to about 95 weight percent, based on the totalweight of the lubricating oil; and wherein the at least one monomericaminic antioxidant is present in an amount from greater than about 2 toabout 10 weight percent, based on the total weight of the lubricatingoil.
 2. The method of claim 1 wherein, in measurements of thelubricating oil by a Sequence IIIH engine test in accordance with ASTMD8111-17, viscosity control and deposit control are improved using aconcentration of the at least one monomeric aminic antioxidant fromgreater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil, as compared to viscosity control anddeposit control achieved using a lower concentration of the at least onemonomeric aminic antioxidant.
 3. The method of claim 1 wherein the atleast one monomeric aminic antioxidant comprises at least oneunsubstituted or hydrocarbyl-substituted diphenyl amine, at least oneunsubstituted or hydrocarbyl-substituted phenyl naphthyl amine, ormixtures thereof.
 4. The method of claim 1 wherein the at least oneoligomeric or polymeric aminic antioxidant is the oligomerization orpolymerization reaction product of at least one unsubstituted orhydrocarbyl-substituted diphenyl amine, at least one unsubstituted orhydrocarbyl-substituted phenyl naphthyl amine, or both at least oneunsubstituted or hydrocarbyl-substituted diphenylamine and at least oneunsubstituted or hydrocarbyl-substituted phenyl naphthylamine.
 5. Themethod of claim 1 wherein the at least one oligomeric or polymericaminic antioxidant comprises:

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.
 6. The methodof claim 1 wherein the at least one monomeric aminic antioxidantcomprises:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₁₉; and/or


7. The method of claim 1 wherein the at least one oligomeric orpolymeric aminic antioxidant is the oligomerization or polymerizationreaction product of

wherein (A) and (B) each range from zero to 10, provided (A)+(B) is atleast 2; R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 toC30 alkyl, q and y individually range from 0 to up to the valence of thearyl group to which the respective R groups are attached.
 8. The methodof claim 7 wherein the at least one oligomeric or polymeric aminicantioxidant is an oligomerization or polymerization reaction productcomprising: (A)(A), (A)(B), (B)(B), (A)(A)(B), (A)(A)(A), (A)(B)(A),(B)(B)(B), (B)(B)(A), (A)(A)(A)(A), (A)(A)(B)(B), (A)(A)(A)(B),(B)(B)(B)(B), (B)(B)(B)(A), (A)(A)(A)(A)(A), (A)(B)(A)(B)(A),(A)(B)(B)(B)(A), or mixtures thereof.
 9. The method of claim 7 whereinthe at least one oligomeric or polymeric aminic antioxidant is theoligomerization or polymerization reaction product formed by anycombination of:

wherein R is H, C₄H₉, C₈H₁₇, or C₉H₉; and/or


10. The method of claim 1 wherein the at least one oligomeric orpolymeric aminic antioxidant is an oligomerization or polymerizationreaction product selected from the group consisting of:

wherein R² is a styrene or C1 to C30 alkyl, R³ is a styrene or C1 to C30alkyl, R⁴ is a styrene or C1 to C30 alkyl, p, q and y individually rangefrom 0 to up to the valence of the aryl group to which the respective Rgroups are attached.
 11. The method of claim 1 wherein the lubricatingoil base stock is present in an amount from about 1 to about 80 weightpercent, based on the total weight of the lubricating oil.
 12. Themethod of claim 1 wherein the at least one monomeric aminic antioxidantis present in an amount from about 4 to about 8 weight percent, based onthe total weight of the lubricating oil.
 13. The method of claim 1wherein the at least one oligomeric or polymeric aminic antioxidant ispresent in an amount from about 0.1 to about 5 weight percent, based onthe total weight of the lubricating oil.
 14. The method of claim 1wherein the formulated oil further comprises one or more of a viscositymodifier, dispersant, detergent, other antioxidant, pour pointdepressant, corrosion inhibitor, metal deactivator, seal compatibilityadditive, anti-foam agent, inhibitor, and anti-rust additive.
 15. Themethod of claim 14 wherein the other antioxidant comprises at least onearomatic amine antioxidant, at least one phenolic antioxidant, ormixtures thereof.
 16. The method of claim 1 wherein the at least oneoligomeric or polymeric aminic antioxidant is formed over time in situduring a Sequence IIIH engine test in accordance with ASTM D8111-17, ora General Motors Oxidation and Deposit Test (GMOD) in accordance withGMW17043, 2^(nd) Edition, May
 2016. 17. The method of claim 1 whereinthe lubricating oil is a passenger vehicle engine oil (PVEO), acommercial vehicle engine oil (CVEO), or a lubricating oil that issubjected to heat and oxidative conditions.
 18. A method forregenerating at least one oligomeric or polymeric aminic antioxidant ina lubricating oil, during operation of an engine or other mechanicalcomponent lubricated with the lubricating oil by using as thelubricating oil a formulated oil, said formulated oil having acomposition comprising a lubricating oil base stock as a majorcomponent; and at least one oligomeric or polymeric aminic antioxidantand at least one monomeric aminic antioxidant, as minor components;wherein the at least one oligomeric or polymeric aminic antioxidantdissipates over time in the lubricating oil during operation of theengine or other mechanical component; wherein the at least oneoligomeric or polymeric aminic antioxidant and the at least onemonomeric aminic antioxidant react to form over time in situ at leastone regenerated oligomeric or polymeric aminic antioxidant duringoperation of the engine or other mechanical component; wherein thelubricating oil base stock is present in an amount from about 1 to about95 weight percent, based on the total weight of the lubricating oil;wherein the at least one oligomeric or polymeric aminic antioxidant ispresent in an amount from greater than about 0.1 to about 10 weightpercent, based on the total weight of the lubricating oil; and whereinthe at least one monomeric aminic antioxidant is present in an amountfrom greater than about 2 to about 10 weight percent, based on the totalweight of the lubricating oil.